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DOI 10.1070/RC2014v83n10ABEH004471
The challenges of the modern society and the growing demand of high-technology sectors of industrial production bring
about a new phase in the development of organic synthesis. A cutting edge of modern synthetic methods is introduction of
functional groups and more complex structural units into organic molecules with unprecedented control over the course of
chemical transformation. Analysis of the state-of-the-art achievements in selective organic synthesis indicates the appearance
of a new trend Ð the synthesis of organic molecules, biologically active compounds, pharmaceutical substances and smart
materials with absolute selectivity. Most advanced approaches to organic synthesis anticipated in the near future can be
defined as `atomic precision' in chemical reactions. The present review considers selective methods of organic synthesis
suitable for transformation of complex functionalized molecules under mild conditions. Selected key trends in the modern
organic synthesis are considered including the preparation of organofluorine compounds, catalytic cross-coupling and
oxidative cross-coupling reactions, atom-economic addition reactions, methathesis processes, oxidation and reduction
reactions, synthesis of heterocyclic compounds, design of new homogeneous and heterogeneous catalytic systems,
application of photocatalysis, scaling up synthetic procedures to industrial level and development of new approaches to
investigation of mechanisms of catalytic reactions.
The bibliography includes 840 references.
Contents
I. Introduction 886
II. Present-day methods for the synthesis of organofluorine compounds 888
III. Metathesis reaction catalyzed by ruthenium complexes 894
IV. Oxidative cross-coupling 899
V. Catalytic atom-economic addition reactions 904
VI. N-Heterocyclic carbene ligands in homogeneous catalysis 908
VII. Development of methods for the synthesis of heterocyclic compounds. Synthesis of pyrrolidine and piperidine derivatives 914
based on cyclic ketimines
VIII. Photocatalysis in modern organic synthesis: design of hybrid semiconductor nanophotocatalysts 923
IX. Approaches of the surface science to the development of new catalytic systems for organic synthesis 927
X. Bimetallic catalysts in organic synthesis 934
XI. Carbon materials in catalysis 940
XII. Heterogeneous catalysts in the industrial production of organic compounds 946
XIII. Studies of the mechanisms of catalytic reactions by the nuclear spin hyperpolarization technique 952
XIV. Preparation of materials for organic electronics 959
XV. Supramolecular gels as a new class of smart materials 964
XVI. Conclusion 970
chemical processes, gave rise to a set of new approaches of into organic molecules. High tolerance for the presence of
organic synthesis. This work was markedly stimulated by functional groups considerably extended the scope of
understanding of the reaction mechanisms at the molecular applicability of these synthetic methods. A milestone in the
level coming from application of advanced hardware and progress of this line of research is the development of
analytic tools.13 ± 18 catalytic cross-coupling processes involving heteroatom
Apart from studies aimed at systematic development of functional groups aimed at the formation of the carbon7
the strategy of classical organic synthesis, new approaches heteroatom bond.
in this field appear and rapidly develop giving rise to whole These catalytic reactions, which have quite recently been
areas of modern chemistry (microwave-assisted reactions, worked out and optimized on the laboratory scale (<1 g of
ultrasonic treatment, microreactor processes, processes in the product), are now actively employed in pilot plants (tens
ionic liquids and gels, reactions in supercritical media and or hundreds killogrammes of a product).14, 19 Of outstand-
some other). ing value is the possibility of targeted transformation of a
A special place among the promising approaches to specified group (atom) in complex functionalized organic
increasing the efficiency of organic synthesis is occupied by molecules. For illustration, several vivid examples can be
implementation of catalytic reaction pathways for desired given, in particular, the Pd-catalyzed Heck reaction at the
chemical transformations. The use of catalytic reactions C(60 ) position to give derivative A, the Pd ± Cu-catalyzed
makes it possible to replace chemicals that are responsible Sonogashira reaction at C(30 ) to afford derivative B, and the
for the formation of hazardous wastes by environmentally Ru-catalyzed metathesis at C(120 ) to form derivative C
safe oxidants (H2O2, O2) and reductants (H2). Moreover, (Fig. 1). The functionalization of a particular carbon atom
catalysis can guide the reaction along a shorter and a more is successfully accomplished with high precision even in
efficient pathway (e.g. direct synthesis without using pro- rather complicated molecules containing many functional
tecting groups) with high selectivity to the target products, groups and reaction sites.
providing the fulfillment of green chemistry principles such For optimization of the cost/efficiency criterion, which
as atomic and energetic efficiency of the chemical reaction. is of prime importance for process scaling up, it is necessary
Catalysis dramatically changed the face of the chemical to develop new synthetic methods requiring a minimum
science in the 21st century and now it plays a leading role in amount of the catalyst. The continuous search for new
increasing efficiency of modern chemical processes. Most catalytic systems carried out in the last decades resulted in
widely used are two types of catalytic processes Ð homoge- the discovery of reactions with ultralow catalyst load (at
neous catalysis by metal complexes (preparation of phar- ppm or ppb level). An exceptionally high activity was found
maceutical substances, drugs and other applications of fine for dynamic catalytic systems with the possibility of adap-
organic synthesis) and the heterogeneous catalysis by metal tive tuning.20, 21
nanoparticles (processing of hydrocarbons, large-scale syn- Yet another promising approach to increase the effi-
theses and most of industrial processes). In recent years, ciency of catalytic reactions in fine organic synthesis is the
organocatalysis has become a new and extremely actively use of specially developed heterogeneous catalysts in which
developing area. the active components are immobilized metal complexes or
Transition metal-catalyzed reactions of carbon7carbon even deposited metal particles. Indeed, heterogeneous cata-
and carbon7heteroatom bond formation have greatly con- lysts have a number of significant advantages over homoge-
tributed to the production of fine organic synthesis prod- neous systems and, therefore, they may be considered more
ucts, pharmaceutical products, natural products, smart valuable for commercialization. In particular, heterogene-
materials and synthetic blocks for drug manufacture. The ous catalysts are non-toxic, can be safely stored and
catalytic cross-coupling reactions allowed for the incorpo- handled, are stable over broad temperature and pressure
ration of diverse aryl, alkenyl, dienyl and alkynyl moieties ranges, have long lifetime and can be easily regenerated and
HN
O Me
OMe O N
HN N S
Cl MeO N
HN Me C(30 )
N
N N Cl
C(60 ) O
H
O N H CO2H
N A N N
Me N
N
Selective inhibitor of NH2
O O H O
ErbB2-promoted B N O
angiogenesis (anticancer activity) O
Inhibitor of cathepsin S cysteine protease O C(120 )
(treatment of immune disorders)
C
Hepatitis C virus NS3 protease
inhibitor (antiviral activity)
Figure 1. Key role of catalytic Heck, Sonogashira and metathesis reactions in the design of complex organic molecules (A , B and C,
respectively) by transformation of specified reaction sites (marked by a circle and an oval). 19
888 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
separated from the reaction medium by filtration or cen- implementation of photocatalysis reactors (light-emitting
trifugation. Furthermore, the use of heterogeneous catalysts diode matrices and solar light). For the goals of selective
opens up prospects for conduction of organic synthesis in organic synthesis, noteworthy are visible light-activated
flow type systems, which are more productive and cost hybrid inorganic semiconductor nanophotocatalysts, which
effective. proved to be good for selective oxidation of organic com-
The present review presents a brief analysis of some pounds (Section VIII).
modern trends of selective organic synthesis in the relevant Recent studies revealed exceptionally high activities of
fields. Each Section starts with brief highlight of the general transition metal clusters and nanoparticles in catalytic
trends in the considered subject matter, which is followed by reactions of selective organic synthesis. Until recently, this
analysis of particular cases of practical implementation and boundary area between the homogeneous and heterogene-
use in organic chemistry. ous catalysis has remained virtually unexplored. Mean-
The review starts with discussion of selective methods while, it is in this area that one should expect the next
for the formation of carbon7heteroatom bonds and trans- upturn in the development of catalysis and the creation of a
formation processes of heteroatomic functional groups. new generation of high-performance catalysts (active, selec-
These functional groups are crucial for organic molecules tive, stable and regenerable catalysts). Investigation of the
to exhibit biological activities (for design of new drugs) and prospects of this trend starts with considering special
practically useful properties (for the development of new approaches to the design of new heterogeneous catalytic
materials). systems for the synthesis of organic compounds (beginning
Section II considers the fine organic synthesis of fluo- of Section IX); then experimental details are considered
rine compounds, which has lately faced new challenges (Section IX.1) and particular examples of practical imple-
calling for fundamentally new approaches. Analysis of the mentation of catalytic processes are discussed (Sec-
state of the art of this field demonstrates that known tion IX.2).
reagents and non-catalytic processes are currently success- The discovery of high activity and selectivity of bimet-
fully combined with new metal-catalyzed and organocata- allic systems (Section X), which have already proved to be
lytic reactions (Section II.1). A vivid example of efficient in cross-coupling, oxidation and reduction (Sec-
introduction of a new catalytic approach into the everyday tions X.1 and X.2), was highly important for fine organic
practice of organic synthesis is metathesis (Section III), the synthesis. Scaling-up of fine organic synthesis methods for
implementation of which is considered in detail in relation commercialization of industrially significant processes
to the preparation of biologically active organofluorine requires special approaches to the development of catalysts
derivatives (Section III.1). (Sections XI and XII) and elaboration of new methods for
The oxidative cross-coupling (Section IV) and atom- real-time monitoring of catalytic systems and investigation
economic addition reactions (Section V) represent new of the reaction mechanisms (Section XIII).
strategic approaches to the formation of carbon7 hetero- The preparation of biologically active compounds and
atom bonds. Particular implementation of the practically application of organic synthesis to solve problems of phar-
demanded reactions is discussed by the examples of C7O maceutical industry are discussed in several sections of the
(Section IV.1) and C7P (Section V.1) bond formation. The review (Sections II ± XII). Yet another practically signifi-
primary attention is paid to the possibility of tuning cant application of fine organic synthesis methods is the
catalytic systems by selecting the catalyst and the ligands fabrication of molecular building blocks for the design of
for controlling the reaction selectivity. new-generation smart materials. The catalytic cross-cou-
As shown by practice, the design of new ligands is a way pling reactions and transformations of heteroatomic func-
of developing versatile metal/ligand structural units, which tional groups have already become irreplaceable tools for
then serve as the basis for various catalysts. In this case, it is the design of materials for organic electronics (Sec-
possible to manufacture versatile catalysts for the formation tion XIV). The development of advanced organic and
of not only carbon7heteroatom bonds but also carbon7 metal-organic materials is also a practically important
carbon bonds. Most successful along this line are N-hetero- application (Section XV).
cyclic carbene ligands (Section VI). A particular application The present review considers selective methods of
of a class of these ligands Ð diaminocarbenes with organic synthesis suitable for transformation of complex
expanded rings Ð resulted in the development of a series organic molecules without affecting the functional groups
of catalysts for cross-coupling, hydrogenation, hydrosilyla- and asymmetric centres already present in the molecule.
tion, hydroboration, hydroamination, arylation, polyme- Therefore, the range of covered reactions is limited to those
rization and for asymmetric synthesis (Sections VI.1 and proceeding under mild conditions (as a rule at 4200 8C),
VI.2). which have been already shown to be tolerant to the func-
Not surprisingly, the modern chemistry of heterocyclic tional groups present in the molecule and applicable in
compounds is actively developing along two lines, the first asymmetric synthesis.
one being targeted synthesis of demanded heterocyclic
compounds (Section VII) and the second one being the II. Present-day methods for the synthesis of
preparation of ligands for catalytic reactions. Particular
methodological approaches to the former line are consid-
organofluorine compounds
ered in Section VII.1, while ligand systems are discussed in The key specific feature of the fluorine atom, which is
Section VI. largely responsible for organofluorine chemistry being a
A significant methodological achievement of recent separate research area, is the ability to crucially change the
years that affected the formation reactions of carbon7 properties of compounds. Indeed, one or several fluorine
heteroatom and carbon7carbon bonds is the design of a atoms being introduced into an organic molecule were
new generation of photocatalysts and a convenient practical found to induce pronounced changes in the chemical and
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 889
physicochemical properties of the compound. In turn, the nated compounds often requires unusual approaches, and
unusual or even unique properties of fluorine compounds studies of the reactivity of these compounds are of funda-
open up a broad scope of practical applications.22, 23 mental interest.
Starting from the mid-20th century, fluorine has played Fluorine is rather abundant in nature as inorganic
an important role in materials science (fluorinated poly- fluorides (the fluorine content in the Earth crust is markedly
mers), and chlorofluoroalkanes have been popular as refrig- higher than the chlorine content!). In view of the high
erants (in particular, in household refrigerators). Somewhat strength of the C7F bond, which is the strongest bond
later, fluorinated ethers were introduced into medical prac- formed by a carbon atom, it is surprising that only a few
tice as general anesthetics. Since the late 1980s, organo- natural fluorinated organic compounds are known.38 This
fluorine compounds have been a necessary component of fact implies that the formation of the C7F bonds under
liquid crystals, which are widely used to manufacture flat natural conditions is difficult and generally defines the
monitors and TV screens.24 problem of using available and convenient metal fluorides
However, the most remarkable feature of fluorine is the for the introduction of fluorine.
ability to modify the biological activity profiles of organic The organofluorine chemistry has developed during the
compounds.25, 26 Indeed, there are numerous examples whole 20th century and the obtained results formed the
where one or several fluorine atoms or a fluorinated group foundation of this area.22, 39 However, in the last 10 ± 15
being introduced in a potential drug molecule substantially years, the number of publications on this topic has
enhance the therapeutic effect or give rise to new types of increased like an avalanche, which is reflected in a number
activity.27 ± 30 Some structures of commercially successful of recent reviews.40 ± 44 Section II.1 presents the key
fluorine-containing drugs 31 ± 34 are shown in Fig. 2. approaches, methods and reagents determining the modern
There is no general answer to the question of how level of organofluorine synthesis. The processes character-
fluorine works. For each particular compound, there are ized by high selectivity and allowing the use of substrates
own causes among which mention may be made of the effect with a broad range of functional groups are considered.
of fluorine on the metabolism rate, a change in the lip- However, this Section does not cover the reactions involv-
ophilicity and an increase in the drug ± enzyme binding ing highly reactive reagents such as fluorine or hydrogen
constant. Currently, *20% of the pharmaceutical agents fluoride, which are, on the one hand, highly dangerous and,
permitted for commercial use contain one or several fluo- on the other hand, can react with almost any functional
rine atoms. This percentage is even higher for agricultural group.45, 46
chemicals (about 30%).35
In recent years, a field of diagnostic medicine tightly II.1. Comparative analysis of methods for the synthesis of
related to fluorine Ð positron emission tomography Ð has compounds with CF3, CF2 and CF groups
been vigorously developing.36, 37 The most important The known methods for the preparation of fluorine com-
parameter for effective use of this method is the quickness pounds can be divided into two types. One type of
of production and isolation of radioactive fluorinated methods, which is discussed in this Section, is based on
products, which represents an additional challenge for the direct introduction of a fluorine atom or a fluorinated
synthetic chemists group into a molecule. The development of these methods
It is evident that the design of new drugs requires that requires new reactions, reagents, catalysts, ligands and, in
preparation methods for diverse fluorine-containing com- some cases, fundamentally new approaches. The second
pounds be available. The conventional reactions used to type includes reactions involving building blocks that
prepare chloro-, bromo- and iodo-derivatives are, most already contain fluorine, in some cases, remote from the
often, inapplicable for fluorination. The synthesis of fluori- reaction centre. These processes are described in more
detail in Section III.
O O F
S O
II.1.a. Methods for the introduction of a CF3 group
F O A popular method for the introduction of a trifluoromethyl
OH O
HO group is nucleophilic trifluoromethylation.47 Unlike classi-
N N H cal organomagnesium and -lithium reagents, the trifluoro-
N O methylated analogues (for example, F3CLi, F3CMgBr) are
Me F H
unstable even at reduced temperatures (778 8C). The most
Levofloxacin O convenient synthetic equivalent of the CF3 carbanion is
(antibiotic) F trimethyl(trifluoromethyl)silane (1) (Ruppert ± Prakash
Fluticasone propionate reagent). Treatment of silane 1 with basic activating
H2N O
(antiasthmatic agent) reagents (fluoride, carboxylate and alkoxide anions) results
S in the generation of a pentacoordinate intermediate, which
O
serves as the source of the trifluoromethyl anion
(Scheme 1).
N N Scheme 1
7
X
CF3 X7 Me
Me3SiCF3 Si Me CF37
1 Me
CF3
Celecoxib (anti-inflammatory
agent) Figure 2. Examples of fluori-
nated medical drugs. X7 = F7, AcO7, ButO7
890 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
Using silane 1, carbonyl compounds 47 ± 49 and imines 50 was carried out. This process includes a double allylic
(and many other compounds with the C N bond) 51 can be = substitution: first, the chiral nitrogen-based nucleophile
easily converted to the corresponding CF3-substituted alco- (L) attacks substrate 2 at the double bond thus generating
hols and amines Ð useful building blocks for medicinal chiral electrophilic intermediate 3, which reacts with silane 1
chemistry (Scheme 2). (Some schemes in the review are under activation by the released carboxylate anion.56, 57
presented in the general form reflecting the possibility of A lot of attention was paid to the cross-coupling of aryl
the processes; excessive detailing was considered inexpe- halides with nucleophilic trifluoromethylating reagents cat-
dient.) Examples of the asymmetric addition of the trifluor- alyzed by transition metal complexes.41 In the case of
omethyl group to aldehydes using the fluoride anion for catalysis by palladium complexes, there is a problem of
activation in combination with the chiral ammonium coun- slow reductive elimination from RPd(L)CF3 . This problem
ter-ion based on cinchona alkaloids were described.52 was solved only in 2010 by using monophosphine biphenyl
ligands in the reaction of aryl chlorides with a silicon
Scheme 2 reagent (Scheme 4).58 Later, this cross-coupling reaction
Me3SiCF3, X7
O OH was extended to vinyl triflates and vinyl nonaflates.59
(1)
R R CF3
Scheme 4
Et3SiCF3, KF,
R2 R2 cat Pd, L
N HN Cl CF3
1, X7 dioxane, 130 8C
R R
R1 R1 CF3
OMe
2 R2 O7
The conduction of electrophilic trifluoromethylation is a
O very difficult task. The presence of three fluorine atoms at
the reaction centre hampers classical SN1 and SN2 reaction
L R1 OR3
Structures 4, 5
L+ F3C F3C
3 I O I O
O +
CF3 O O CF3
Me3SiCF3,
R2 O7
R1 OR3 (1)
4 5
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 891
mechanisms. In 2006, reagents 4 and 5 based on trivalent In recent years, the interest in free radical trifluorome-
iodine Ð Togni reagents Ð were proposed (Scheme 6).64, 65 thylation processes has substantially increased.42 Indeed,
unlike the carbocation or carbanion, the trifluoromethyl
Scheme 6 radical is generated rather easily. This can be done under
O Me either oxidative or reductive conditions (Scheme 9). The
N trifluoromethyl radical can react with various p-nucleo-
5,
Bn
N
. CF
3CO2H
O
philes (alkenes, aromatic compounds) to give products of
O (20%)
H CF3-group substitution for hydrogen. Thus, CF3-contain-
R R
CuCl (5%), CHCl3, 720 8C ing compounds can be prepared without preliminary func-
CF3 tionalization of the substrate. However, the problem of low
(ee >93%) regioselectivity of the radical trifluoromethylation of sub-
stituted aromatic compounds remains unsolved in most
These reagents proved to be efficient for electrophilic cases.
trifluoromethylation of a very broad range of substrates. Scheme 9
Besides C-nucleophiles (1,3-dicarbonyl compounds, a-nitro-
esters, aromatic compounds), this reaction may involve F3C F3C
O
thiols, phosphines, alcohols and azoles. Scheme 6 depicts I O I O
CF3 I, or CF3 S Cl, or , or
an example of asymmetric trifluoromethylation of alde- O
hydes with compound 5 in the presence of the MacMillan O
catalyst.66 4 5
A new direction is related to the ability of some electro-
philic trifluoromethylating reagents to transfer a cationic e
CF3 group to a transition metal. This increases the oxida- O
.
tion state of the metal, which considerably promotes the CF3 S CF3
7e
reductive elimination. Presumably, the trifluoromethylation OM
of boronic acids with 5 in the presence of copper salts occurs
by this mechanism (Scheme 7).67, 68 In the palladium chem- . CF3 CF3 CF3
CF3 [O]
istry, a cycle based on the PdII/PdIV pair was also proposed . H + H
for CH-trifluoromethylation of aromatic compounds.69 In 7H+
the latter case, the Umemoto reagent was used as the source R R R R
of the CF3 cation (6) (see Scheme 7).
Scheme 7 A special but still important case of synthesis of
5, CuI (5%), phen (10%) CF3-containing compounds is the introduction of the
Ar B(OH)2 Ar CF3
K2CO3, 358C, 14 h 2,2,2-trifluoroethyl substituent, which can be performed by
a nucleophilic substitution reaction (Scheme 10). Methods
of Pd-catalyzed cross-coupling involving boronic acids or
+
S
pinacolyl boronates and trifluoroethyl iodide were pro-
BFÿ
4 Pd(OAc)2 (10%), posed; for this reaction to occur, the presence of a sterically
R (6) CF3 Cu(OAc)2 (1 equiv.)
R
hindered phosphine ligand, either bidentate Xanthphos or
N N
110 8C, 48 h monodentate SPhos, is required.72, 73 However, reactions
CF3 involving 2,2,2-trifluoroethyl organometallic reagents 8,
which are prone to b-elimination, are still unknown. Just
Starting from 2010, studies of reactions involving cross- recently, stable organoboron compounds of this type [8,
coupling of a nucleophilic component with a nucleophilic M = B(OR)2] were obtained but cross-coupling reactions
trifluoromethylation reagent in the presence of an oxidant with these reagents have not been studied as yet.74
(additional reagent or air oxygen) have been rapidly devel-
oping (Scheme 8). For example, a combination of simple Scheme 10
terminal acetylenes with silane 1 in the presence of KF and Nu
F3C I F3C Nu
oxygen affords, in one step, CF3-substituted acetylenes 7,
which are very difficult to prepare by any other method.70 F3C I CF3
Similarly, heterocyclic compounds containing a relatively Ar B(OR)2 Ar
acidic hydrogen atom can be trifluoromethylated in the cat Pd0, Xanthphos or SPhos
presence of a silver salt as an oxidant (see Scheme 8).71
F M F
F
Scheme 8 7MF
CuI (20%), phen (20%) F 8 F
R + Me3SiCF3 R CF3
KF, air, DMF, 100 8C
1 7
II.1.b. Methods for the preparation of compounds with a CF2 group
R2 R2 The most general approach to the formation of a CF2
R1 1, Cu(OH)2 (10%), moiety is direct transformation of a carbonyl compound
R1
phen (10%)
CF3 (aldehyde or ketone) according to the deoxofluorination
KF, AgNO3, ClCH2CH2Cl,
N N reaction (Scheme 11).75 However, a considerable drawback
80 8C
of this process is difficulty of handling of fluorine reagents
R3 R3
(toxicity of sulfur tetrafluoride; detonation susceptibility of
892 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
sulfotrifluorides 9). Recently, less hazardous reagents 10 76 bonds, whereas the addition to electron-deficient alkenes is
and 11 77 were proposed. Nevertheless, deoxofluorination less efficient.
implies, by its nature, fairly drastic reaction conditions, Scheme 13
F
which narrows down the range of functional groups that F
F F
may be present in the substrate. C
Scheme 11 R
R
O F F
reagent F
F F F
R1 R2 R1 R2 C
R
R
=SF2 BFÿ4 (10),
+
The reagent is SF4 ± HF, R2NSF3 (9), R2N
O O O O
Me Me3Si X
X S
OM F OY
But SF3 CF2 sources: , ,
F F F F F F
Me (11) (Y = SiMe3, Me) (X = F, Cl, Br)
(X = Cl, Br)
Often, the target compounds are prepared by function- 1,1-Difluoroalkenes 13 are prepared most often by the
alization of accessible compounds that already have a CF2 Wittig reaction (Scheme 14). However, the corresponding
group.78, 79 As simple examples, of note are halodifluoro- phosphonium ylide 14 is unstable and is generated in situ
acetic acids (XCF2CO2H; X = Cl, Br) and their derivatives from dibromodifluoromethane 86 or from zwitter-ionic
and some difluoroalkanes (CF2Br2, ClCHF2), although the reagent 15, which is easily formed from bromodifluoro-
availability of the latter compounds can be considerably acetic acid.87
restricted by the Montreal Protocol due to ozone layer Scheme 14
depletion.
F
Methods based on difluorocarbene reactions are rather PPh3 F
efficient.44 In particular, an approach to the synthesis of O F
(14)
difluoromethylene compounds from three components Ð a R R F
nucleophile, difluorocarbene and an electrophile Ð has 13
been proposed recently (Scheme 12).80 The possibility of
independent variation of the nucleophile and the electro- Ph3P + CF2Br2
F
phile makes this method quite versatile. This approach was O PPh3
demonstrated by a number of examples where organozinc +
Ph3P F
compounds served as nucleophiles and bromine, iodine, O7 14
proton and allyl halide were the electrophiles. Note that F F
with an allylic electrophile, three-component coupling fur- 15
nished two C7C bonds.81 In the reactions with organozinc
reagents, (bromodifluoromethyl)trimethylsilane (12) in the
presence of the acetate anion was used to generate difluor- For the preparation of functionalized compounds with a
ocarbene. CF2 group, a series of heteroorganic (including organo-
Scheme 12 metallic) reagents containing both standard carbon func-
F F F F tional groups (ester,88 nitrile 89) and substituents based on
C
chalcogenides,90 phosphorus 91 and even silicon 92 have been
Nu E Nu E devised (Fig. 3). The presence of these substituents opens up
prospects for the subsequent activation of the carbon7
F F F F F F
C reagent heteroatom bond (C7S, C7P, C7Si) by heterolytic and
R ZnBr
R ZnBr R E
homolytic mechanisms, which provides a broad range of copper and silver) and, probably, includes the initial for-
difluoro-substituted products. mation of the bond between the fluorine atom and the
transition metal followed by reductive elimination.
II.1.c. Methods for the preparation of compounds with a C7F
group Scheme 17
A classical method for the introduction of a fluorine atom
R R
into the aromatic ring is thermolysis of diazonium tetra- M `F+' F
fluoroborates (Schiemann reaction).93 However, this
method is potentially hazardous especially on an industrial
scale due to low stability of diazonium salts. Meanwhile, the M = Li, MgX, B(OR)2, SnR3;
direct nucleophilic substitution of fluoride ion for the
chloride ion, so-called Halex process is applicable only to Cl
O O O O
a narrow range of substrates.94 N+
`F+' = XeF2, + , S S , +
N Ph N Ph N
Replacement of the phenolic hydroxy group by a fluo- TfO7
2 BFÿ
4
rine atom by deoxofluorination is difficult to implement, F F F
and standard fluorine ± sulfur reagents used for aliphatic Selectfluor NFSI
alcohols prove to be inefficient. The most reactive reagent
for the deoxofluorination of phenols is difluoroimidazoline Electrophilic fluorinating reagents have started to be
16, which is suitable only for phenols containing electron- used in enantioselective processes catalyzed by transition
donating substituents in the ring (Scheme 15).95 metals or under organocatalysis. Scheme 18 shows the
Scheme 15 electrophilic fluorination of substrates 17 with chiral phos-
phoric acid 18 functioning as the asymmetric inductor.
R R Presumably, salt 19 containing an achiral N7F group and
OH CsF (3 equiv.) F
+ N N two chiral counter-ions serves as the enantioselective
Ar Ar 80 ± 110 8C, 3 ± 20 h reagent.100 In this reaction, high enantiomeric excess values
F F can be achieved, although the chiral inductor has no
16 covalent bond with either substrate 17 or the fluorinating
Ar = 2,6-Pri2 C6H3
reagent.
Scheme 18
In the last five years, methods for C7F bond formation
based on the transition metal chemistry have been rapidly O Ar F
18 (5%), Selectfluor (1.25 equiv.)
developed.96 The fluorine atom substitution for the triflate O
leaving group was accomplished under palladium catalysis NH Me2N NMe2 Ar
O O
in the presence of sterically crowded monodentate phos- 17 (1.1 equiv.),
N
phines (Scheme 16).97 An alternative method includes 720 8C, 24 h (ee >87%)
replacement of the iodine atom by fluorine on treatment
with an excess of copper(I) triflate and silver(I) fluoride at Pri
H17C8
high temperature.98
Pri
Scheme 16 O O * O O
18 = P = P
R O OH
OTf Pri O OH
a
R H17C8
F Pri
R
I Cl
b * O O + O O *
N
P + P
O7 N
O 7O
O
Pd0 ± R3P,
(a) CsF, cat. 80 ± 130 8C, 14 h; F 19
(b) (ButCN)2CuOTf (3 equiv.), AgF (2 equiv.), DMF, 140 8C, 22 h
A new, in principle, method for the preparation of Academician O M Nefedov and co-workers 101 ± 104 pro-
aromatic fluorides comprises electrophilic fluorination of posed an interesting approach to the synthesis of fluoro-
the nucleophilic carbon ± element bond (Scheme 17). Origi- aromatic compounds, fluoroalkenes and fluorodienes,
nally, quite expensive xenon difluoride was used. A sub- comprising the cycloaddition of fluorine-substituted car-
stantial progress along this line is related to the appearance benes to unsaturated substrates and the subsequent skeletal
of reagents with a nitrogen7fluorine bond,99 although they rearrangement of cyclopropanes involving three-membered
are prepared using elemental fluorine. The Selectfluor and ring opening, resulting in new structures with the fluorine ±
NFSI reagents are stable crystalline compounds convenient carbon bond being retained. The process is conducted in the
for handling and are sold by many companies at reasonable flow mode. This method can be efficiently used to prepare
prices. The reaction of the organometallic substrate with an fluoroaromatic compounds (aromatization is attained upon
N-fluorinating reagent can occur as a direct nucleophilic elimination of hydrogen halide) (Scheme 19).101 Indeed,
attack on the fluorine atom (for M = Li, MgX). However, various mono- and difluoroarene products (including
in some cases (for boron and tin compounds), the reaction is 2,3-difluoronaphthalenes inaccessible by other methods)
catalyzed by transition metal complexes (palladium, nickel, can be obtained from readily available starting compounds.
894 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
F
18F
(76%)
CuCl (5%), Cl Cl
LiCl (5%)
+ is protein
MeCN, 80 8C
F (3 : 1) F
Thus, unlike the CF3 group, which can be introduced
CHCl2F CuCl
into the molecule by a variety of reported methods, there
only a few methods for the precise and highly selective
KOH (aq.), BnNEt3Cl MeCN, 80 8C
introduction of fluoro- and difluoro-substituents. Conduc-
tion of nucleophilic substitution by the SN2 mechanism
Cl F
Cl using fluorine-containing nucleophilic reagents remains an
F unsolved problem.
A separate topical direction is synthesis of compounds
Skeletal rearrangements of methoxy-substituted gem- with a CF2 group. For example, it is difficult to prepare
fluorochlorocyclopropanes can also be used to prepare compounds containing a halodifluoromethyl group (CF2X,
fluorine-substituted a,b-unsaturated aldehydes, ketones X = Cl, Br, I) using existing reactions, and the correspond-
and methoxy-substituted fluorodienes.105, 106 ing carbanions are quite unstable.
The fluorine chemistry has started to play an important
role in the positron emission tomography (PET) based on III. Metathesis reaction catalyzed by ruthenium
the use of isotopes that decay to give off positrons.36, 37
Among these isotopes, 18F with the half-life of 109.7 min is
complexes
most convenient. After injection of a substance containing The previous Section gives comparative analysis of various
18F into the blood, it is possible to determine the exact methods for the introduction of fluorine-containing groups
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 895
into organic molecules. The present part of the review their unique ability to selectively inhibit several important
considers the catalytic methods of transformation of build- enzymes, while exhibiting various types of biological activ-
ing blocks, which already contain fluorine. Extremely broad ity.121
possibilities for the conversion of fluorine-containing Thus, development of selective methods for the synthesis
organic molecules are provided by metathesis. of new fluorine-containing a-amino acids of cyclic structure
During the last decade, the metathesis of alkenes as a by intramolecular metal-catalyzed metathesis transforma-
significant method for the formation of new carbon ± car- tions is of considerable fundamental and applied value.
bon bonds has become one of the most swiftly developing
fields of organic chemistry. This process, which was III.1. Intramolecular metathesis in the synthesis of cyclic
rewarded by the Nobel Prize in 2005, has already made an fluorine-containing a-amino acids and their derivatives
inestimable contribution to the synthesis of physiologically III.1.a. Metathesis of fluorinated dienes
active natural compounds, drugs, diverse functional materi- The metathesis of linear 1,7-dienes containing an a-amino
als and polymers.108 ± 113 acid skeleton was first employed by Grubbs 122 in 1996 to
The discovery of effective ruthenium carbene complexes prepare dehydropipecolic acid (n = 1, Scheme 22). It was
distinguished by high stability with respect to air moisture found that the corresponding five-membered derivatives Ð
and oxygen and to various functional groups resulted in dehydroprolines Ð cannot be synthesized with catalysis by
elaboration of a number of important synthetic processes the carbene complex G-I (see Fig. 4): due to the acidic
such as ring closing metathesis (RCM), cross metathesis nature of the a-proton in the initial 1,6-dienes (n = 0,
(CM), ring opening metathesis polymerization (ROMP), see Scheme 22), the reactions afford only linear a,b-unsatu-
acyclic diene metathesis (ADMET) and alkene ± acetylene rated oligomers. More recently, this strategy was success-
metathesis.114 ± 117 The use of Grubbs ruthenium catalysts fully used by other research teams to prepare six-, seven-
(Fig. 4) provided the unique possibility to predict and and eight-membered amino acid derivatives (n = 1 ± 3,
embody innovative and environmentally friendly synthetic see Scheme 22).123, 124
strategies with minimum time, energy and money expendi- Scheme 22
tures.
H
R2O2C
(R1 = H)
PCy3 R1 (n = 0) N
Cl N N N N PG
Mes Cl Mes Mes Cl Mes
Ru R2O 2C n
Cl N R1
Ph Ru Ru 2O C
PCy3 Cl PG [Ru] R 2
Ph Cl n
PCy3 (n = 173) N
O
G-I PG
G-II
H-II PG is protecting group; [Ru] = G-I, G-II, H-II
Cy is cyclohexyl, Mes is 2,4,6-Me3C6H2
Figure 4. Commercially available catalysts for alkene metathesis: Ring closing metathesis was first used in the synthesis of
Grubbs catalysts of generations I (G-I) and II (G-II), Hoveyda ± fluorine-containing cyclic a-amino acids in 1998.125 The
Grubbs catalyst of generation II (H-II). starting di- and trifluoromethyl dienes were prepared
under mild conditions by amidoalkylation of the corre-
sponding C-nucleophiles with highly electrophilic fluori-
In the chemistry of amino acids and peptides, the use of nated methyl pyruvate imines. The subsequent cyclization
intramolecular metathesis resulted in effective synthesis of was easily accomplished at room temperature in the pres-
cyclic derivatives, which are currently widely used in the ence of 5 mol.% catalyst G-I to give metathesis products in
design of new potential drugs.111 First of all, this is due to high yields. The absence of the a-proton ensured the
the fact that the introduction of cyclic a-amino acids into formation of previously inaccessible five-membered proline
strategic sites of peptides secures the amide bonds in unique derivatives (n = 0, m = 1, Scheme 23).126
conformations needed to maximize the biological activ- Scheme 23
ity.118 XF2C XF2C
Meanwhile, it is well known that fluorine-containing XF2C CO2Me
MeO2C MeO2C
a, b n c n
analogues of natural biologically active compounds often
N N N
demonstrate unique physiological activity.22, 32, 119 In the PG PG m PG m
last decade, modification of peptides and proteins by (56% ± 75%) (85% ± 97%)
introducing fluorine-containing a-amino acids and their
functional derivatives has been successfully performed.
X = F, Cl; PG = Cbz, Boc, SO2Ph (Cbz is benzyloxycarbonyl,
These modifications lead, most often, to higher lipophilic-
Boc is tert-butoxycarbonyl); n = 0 ± 2; m = 1, 2;
ity, proteolytic and conformational stability, considerably
(a) RMgBr (R is vinyl, allyl, homoallyl), THF, 778 8C;
improving the transport characteristics of potential
(b) RBr (R is allyl, homoallyl), DMF, 0 8C;
drugs.120 Moreover, owing to the presence of fluorine
(c) G-I or G-II (3 mol.% ± 5 mol.%), CH2Cl2, 20 8C
atoms, it is possible to monitor the chemical environment
of fluorine-containing residues and to perform conforma-
tional analysis and study the metabolism of peptides by 19F 2-Trifluoromethyl-substituted 4,5-dehydropipecolic
NMR spectroscopy. In addition, a-amino acids containing acids containing additionally an alkenyl substituent in the
fluorine atoms in the b-position attract attention due to 4-position can be prepared by combined ring opening Ð
896 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
ring closing metathesis (ROM ± RCM).127 The synthesis of macrocyclic compounds and other biologically important
the starting aza-1,7-dienes containing one of the double derivatives.128, 129 A characteristic feature of intramolecular
bonds in the ring comprises the ene reaction of methyl ring closing enyne metathesis is that the formation of a new
trifluoropyruvate imine with methylidenecycloalkanes and C7C bond occurs without the loss of the carbon skeleton
subsequent N-allyllation with sodium hydride-induced and results in cyclic 1,3-dienes with one double bond in the
deprotonation. The aza-1,7-dienes obtained in this way ring, which are widely used to form polycyclic systems.
readily undergo carbene complex G-I-catalyzed rearrange- However, the RCEYM synthesis of cyclic 1,3-diene-
ment of the carbon skeleton, which includes opening of containing a-amino acids often gives unsatisfactory results.
cycloalkene and closure of a new heterocycle, resulting in On the one hand, this may be due to catalyst inhibition
the desired dehydropipecolinates with an alkenyl substitu- upon coordination of the nucleophilic nitrogen atom to the
ent the length of which can be controlled by varying the ring metal centre. On the other hand, metathesis of terminal
size in the starting methylidenecycloalkane (Scheme 24). enynes often gives low product yields due to poisoning of
the active catalytic species in the secondary metathesis
Scheme 24 processes of diene intermediates.130
F3C
Taking into account the above-indicated features, we
MeO2C studied metathesis of 1,6- and 1,7-enynes containing
F3C CO2Me 1)
n [Ru], rt a-XCF2-a-amino acid moieties. The starting enynes can be
N
N 2) AllBr, NaH PG n
obtained either from the corresponding imines 131 similarly
PG to dienes or from fluorinated diazocarbonyl compounds by
(77% ± 85%) [2,3]-sigmatropic rearrangement of the allyl group in nitro-
F3C
MeO2C
gen CF3 ylides (Scheme 26).132
n Scheme 26
N
PG (74% ± 86%) R
XF2C CO2Me 1) R MgBr XF2C
PG = Cbz, Boc, SO2Ph; n = 1, 2 2) AllBr, NaH
MeO2C
N N
PG PG
The catalytic cycle, resulting in the rearrangement of the
carbon skeleton occurs, apparently, in the following way: (42% ± 78%)
four-membered metal ring A formed initially is fragmented
with evolution of a styrene molecule to give carbene com- N
plex B, which undergoes intramolecular cyclization to give F3C CO2Me Me MeO2C [2,3]
+
unstable [2+2]-cycloadduct C. The latter rearranges into a Cu(F3-acac)2 (5 mol.%),
7
N
new ruthenium complex D, which in turn undergoes cross- N2 PhMe, D F3C Me
metathesis with a styrene molecule occurring in the reaction
area to give stable reaction products and a catalyst molecule F3C
for a new catalytic cycle (Scheme 25). MeO2C
Scheme 25 N
F3C Me
MeO2C (76%)
N n
PG F3-acac is 1,1,1-trifluoroacetylacetonate
F3C
MeO2C Ph As a result, it was found that aza-1,6-enynes cyclize only
N n
Ru in the presence of 5 mol.% ± 8 mol.% of the allenylidene
PG ===
ruthenium complex [Ru C C CPh2(Cl)(PCy3)(p-cym-
A Ph ene)]+TfO7, which was deliberately synthesized from the
F3C
readily accessible precursor [RuCl(PCy3)(p-cyme-
Ru ne)]+TfO7 and the alcohol HC:CCPh2OH. The meta-
MeO2C
Ph thesis products obtained in moderate and good yields were
N Ru
PG
B Scheme 27
R
XF2C [Ru]
F3C
Ru MeO2C
MeO2C PhMe, 80 8C
n N
N F3C n
PG
PG D MeO2C CO2Et
F3C N Ru R
PG R CO2Et
MeO2C C
n XF2C EtO2C CO2Et
N XF2C
PG MeO2C N DDQ, PhMe, 110 8C
MeO2C N
PG PG
III.1.b. Metathesis of fluorinated enynes (40% ± 70%) (40% ± 52%)
Ring closing enyne metathesis (RCEYM), like diene meta-
X = F, Cl; PG = Cbz, Boc, SO2Ph; R = H, Bun, CH2OMe;
thesis, has been rapidly developed in recent years and has
acquired importance in the synthesis of carbo-, hetero- and ===
[Ru] = [Ru C C CPh2(Cl)(PCy3)(p-cymene)]+TfO7
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 897
F3C
MeO2C G-II or H-II R = Ph (78% overall yield), 4-MeC6H4 (74%)
N PhMe, 70 8C
Me the alkenyl group exclusively in the Z-configuration,
F3C whereas reactions with ethyl diazoacetate give products
F3C MeO2C with the E-configured alkenyl group.134
MeO2C + Scheme 31
N Me
N Me N F3C
Me CO2Me MeO2C n
(20%) (40%) CF3 N
PG
F3C H
Since cross-metathesis of 1,1-disubstituted alkenes is N2CHSiMe3 MeO2C n
known to be a challenging task requiring either drastic N SiMe3
Cp*Ru(cod)Cl (5 mol.%),
conditions or more active catalytic systems,117 the decision PG
Et2O, rt
was made to introduce an additional substituent to the aza- (53% ± 75%)
1,7-enyne triple bond; then the RCEYM step will give
F3C H
1,1-disubstituted alkene, which will suppress the undesir-
N2CHCO2Et MeO2C
able side homo-cross-metathesis reaction. A number of new n
with the catalyst to give carbene complex E, which reacts opment of efficient catalytic processes for the synthesis of
with the substrate by the classical enyne metathesis mecha- new TIC derivatives is of obvious fundamental and applied
nism up to the formation of intermediate H interest.
(E ? F ? G ? H), and after that, the pathway becomes An original approach was proposed to the synthesis of
different. In particular, intermediate H does not give off CF3-TIC derivatives 139 and their phosphorus analogues 140
the corresponding carbene complex (as in the enyne meta- comprising regioselective co-trimerization of aza-1,7-diynes
thesis) but undergoes instead reductive elimination to give with terminal acetylenes catalyzed by the Grubbs ruthenium
unusual bicyclic products. The observed stereochemistry of complex (G-II). The starting trifluoromethyl-aza-1,7-diynes
the alkenyl moiety may be related to the sterically more were prepared from the imines CF3(X)C N7PG =
favourable arrangement of the trimethylsilyl (TMS) and [X = CO2Me, P(O)(OEt)2)] 141 using the following synthetic
pentamethylcyclopentadiene groups in intermediate F, sequence: (i) the reaction of the imine with propargylmag-
namely, in anti-positions relative to each other. Meanwhile, nesium bromide; (ii) the introduction of the aryl substituent
it cannot be ruled out that the interaction between the at the terminal triple bond by means of Pd-catalyzed cross-
neighbouring chlorine atom and the TMS group can also coupling with aryl iodides; (iii) N-propargylation of the
be responsible for the reaction stereochemistry (Scheme 32). Sonogashira reaction products during deprotonation of
sodium hydride (Scheme 33).
III.1.c. Metathesis transformations of fluorinated diynes. Scheme 33
Co-trimerization of diynes with acetylenes in the synthesis of
F3C X F3C Ar
1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid derivatives a
F3C
b, c X
The intra- and intermolecular cyclotrimerizations of acety- NH
N X N
lenes catalyzed by transition metal complexes have been PG
widely spread during the last two decades as a versatile PG PG
method for the synthesis of substituted aromatic and (65% ± 82%) (53% ± 79%)
heteroaromatic compounds. Catalysts based on transition
metal complexes, most often, cobalt and rhodium, were X = CO2Me, P(O)(OEt)2; PG = Boc, Cbz, Ts;
successfully used in the alkyne cyclotrimerization serving as Ar = Ph, 2-MeC6H4, 4-MeC6H4, 4-MeOC6H4, 4-O2NC6H4;
the key step for the synthesis of a series of biologically (a) Ð HC:CCH2Br, Mg, HgCl2, Et2O, 778 8C;
important structures, including natural compounds.135 (b) ArI, PdCl2(PPh3)27CuI (5 mol.%), organic base, rt;
However, only a few examples of application of this strategy (c) NaH, HC:CCH2Br, DMF, 0 8C
to prepare a-amino acid derivatives were reported, and data
on the synthesis of fluorine-containing amino acids and A study of the Ru-catalyzed cyclotrimerization of aza-
their phosphorus analogues are totally absent. 1,7-diynes with various alkynes (acetylene, hex-1-yne, oct-1-
It is known that the tetrahydroisoquinoline moiety is yne and phenylacetylene) ascertained that reactions with
encountered in many organic compounds that exhibit var- terminal acetylenes occur on moderate heating in dichloro-
ious types of biological activity including antihypertensive, ethane (DCE) in the presence of 5 mol.% of the second-
antimalarial and antitumour activities. Among these, generation Grubbs catalyst (G-II) and lead to the corre-
1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (TIC), sponding bicyclic derivatives with high meta-selectivity and
being a conformationally rigid analogue of phenylalanine, in good yields (Scheme 34). In all cases, the content of the
attracts particular attention as an important component of meta-isomer was above 92%, and in the case of the 2-MeO-
highly selective enzyme inhibitors and integrin and d-opioid phenyl substituent, it was >97%.
receptor antagonists with a broad spectrum of pharmaco- Scheme 34
logical activity.136, 137 The most vivid example of using the
TIC pharmacophore for the drug design is the discovery of N N
Mes Mes
Accupril1,138 which is currently used to treat hypertension Cl
and congestive heart failure (Fig. 5). Therefore, the devel- Ru
F3C Ar Cl Ph
X PCy3
R2 +R
N DCE, 50 8C, 3 h
Ph
R1(O)C PG
R4 HO2C
N Ar Ar
R3 F3C F3C
EtO N R
N X X
+
Enzyme inhibitors and H N N
O O R PG
integrin and opioid PG
Accupril 1 meta ortho
receptor antagonists (62% ± 82%)
R2
(R1O)2(O)P PG = Boc, Cbz, Ts; Ar = H, Ph, 2-MeC6H4, 4-MeC6H4, 2-MeOC6H4,
R4 4-O2NC6H4; X = CO2Me, P(O)(OEt)2; R = H, Ph, Bun, n-C6H13
N
R3
Obtained in 2013 The presumptive mechanism of cyclotrimerization
includes the preferred addition of the ruthenium carbene
Figure 5. 1,2,3,4-Tetrahydroisoquinoline-3-carboxylic acid deriv- complex to the terminal triple bond of aza-1,7-diyne to
ative. afford intermediate I, this step being facilitated by the
coordination of ruthenium to the remaining triple bond.
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 899
This is followed by a cascade of well-known intra- and ties.147, 148 Therefore, the search for new, in principle,
intermolecular metathesis steps J ? K ? L, which ends in ruthenium-based catalytic systems with enhanced character-
the release of the ruthenium benzylidene active species and istics,149, 150 first of all the activity and selectivity, is a highly
predominant formation of the meta-isomer. The selective topical line of research of modern chemical science.
[2+2]-addition of the terminal acetylene to the Ru C =
bond of intermediate J, resulting in the formation of
ruthenacyclobutene K, is responsible for the observed
IV. Oxidative cross-coupling
chemo- and regioselectivity of the process (Scheme 35). Currently, there is no universal way of C7F bond forma-
tion; furthermore, the classical cross-coupling reactions
Scheme 35 proved inapplicable for this purpose. It is worth noting
F3C that for a number of other carbon7heteroatom bond
Ar
X formation reactions, versatile synthetic procedures were
F3C
N Ar elaborated within a general approach. This Section dis-
PG X
Ru cusses the coupling reactions giving C7O bonds. This is
N
PG Ar
followed by discussion of atom-economic addition reactions
F3C (Section V) and versatile catalytic systems based on N-het-
preferred
X Ru erocyclic carbenes as ligands (Section VI).
addition
I Ph N The study of oxidative cross-coupling (cross-dehydro-
PG genative coupling, CDC reaction) is among the key lines of
Ru J research in organic chemistry. As a rule, these are reactions
Ph
Ph in which two different molecules are linked by a new bond,
each giving off a hydrogen atom. The oxidative cross-
R coupling provides the formation of a new bond with almost
Ar F3C Ar
F3C R the maximum possible atom efficiency and does not require
X Ru additional synthetic steps of introduction of functional
X
R N groups that are necessary for other approaches to cross-
N PG
PG
coupling (Hal, OTf, BR2 , SiR3 , SnR3 , ZnHal). Thus,
Ru
Ph oxidative coupling is a promising approach to decreasing
L Ph K the amount of by-products and decreasing the number of
Ar
F3C steps of the organic synthesis.151 ± 154 The key problem faced
X by implementation of the oxidative coupling is to ensure the
N process selectivity and minimize the side oxidation reac-
PG R tions.
The oxidative coupling processes are of not only prac-
tical but also of considerable fundamental interest for
N N
Mes Mes research. Implementation of these processes requires the
Ru Cl
= + PCy3
Ph Ru discovery of new aspects of reactivity of organic com-
Cl Ph pounds, invention of new oxidative systems and study of
their properties, and accurate choice of reaction conditions.
Note that new fluorine-containing a-amino acids and Among oxidative cross-coupling reactions, C7C cou-
their derivatives prepared by ring closing metathesis hold pling has been studied most comprehensively, while C7O
good promise for the use in bioorganic and medicinal coupling has been less studied.151 ± 154 Performing the oxi-
chemistry for modification of biologically active peptides dative C7O cross-coupling is a challenging task due to
and are of interest by themselves for biological activity some features of the chemical behaviour of the O-compo-
assays. nents used for coupling. A new C7O bond may be formed
Generally, despite the substantial achievements in the from O-nucleophile, O-electrophile or O-radical. Most
metathesis, some problems of intra- and intermolecular compounds containing an OH group (O-components) have
metathesis transformations remain unsolved. First of all, rather low nucleophilicity, especially in neutral or acidic
this concerns the regio- and stereoselectivity of reactions, medium in which most oxidative systems used for coupling
especially in the metathesis involving polyfunctional unsa- are reactive. O-Electrophiles are rarely used in reactions
turated compounds containing internal double (RCM proc- giving a C7O bond between two molecules, being repre-
ess) and terminal triple (RCEYM process) bonds. Further- sented by peroxides having specific structure such as
more, due to the thermodynamic nature of metathesis, the (p-nitrophenyl)sulfonyl peroxide 155 and benzoyl perox-
Z-selective alkene metathesis is still a highly problematic ide 156 Ð reactions with these compounds are beyond the
reaction. The use of most of commercially available cata- scope of this Section of the review. O-Radicals are usually
lysts usually furnishes a difficult-to-separate Z- and generated under drastic conditions, they are highly reactive
E-alkene mixture in which the more thermodynamically and unstable; reactions involving O-radicals are often non-
favourable E-isomer predominates.142 This fundamental selective and are accompanied by the formation of alcohols,
problem of the alkene metathesis markedly restricts its carbonyl compounds and fragmentation products.
industrial implementation. Solution of this problem can
lead to creation of industrially important processes for IV.1. Formation of the carbon ± oxygen bond
utilization of by-products of petroleum cracking,143, 144 Alcohols or carboxylic acids are used most often as the
alternative energy sources based on bioresources 145, 146 O-components for the C7O coupling; coupling reactions
and new stereoregular polymers with unique proper- with sulfonic acids, hydroxylamine derivatives and perox-
900 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
ides are also encountered. The C-components are repre- (Scheme 37, here and below in this Section, fragments of
sented by compounds containing directing functional reactant and product molecules are shown).158 Presumably,
groups (amide, nitrile, heteroaromatic, oxime or azo reactions proceed through the formation of intermediates
group) and by substrates containing activated C7H bonds with the C7Pd7OR moiety, which undergo reductive
(carbonyl compounds, ethers, compounds with benzyl or elimination to give the C7O coupling product. A general
allyl moiety). By directing group is meant a functional drawback of the method is the use of an excess of the
group that facilitates the oxidative coupling and determines O-component of coupling, which makes this approach
its regioselectivity (for example, by means of complexation unsuitable for coupling involving alcohols or acids with
with the metal catalyst) but is not changed itself during the complex structures.
reaction. In the presence of directing groups, the alkyl groups of
An example of using the pyridine moiety as the directing the molecule can be involved in oxidative coupling with
group for oxidative alkoxylation of aryl and benzyl CH alcohols or carboxylic acids. An example is alkoxylation of
groups is presented in Scheme 36.157 Presumably, the cop- N-(quinolin-8-yl)amides under the action of iodine(III)
per ion is inserted into the C7H bond of the aromatic ring, catalyzed by palladium acetate (Scheme 38).159 Primary,
the CuII complex thus formed is oxidized by silver(I) ions to secondary and tertiary alcohols, including those containing
a CuIII complex and the C7O bond is formed upon functional groups can be involved in this reaction, the yields
reductive elimination. The drawbacks of the method are being up to 91%. A drawback of the method is the use of an
the use of large amounts of silver triflate and alcohol excess of the alcohol and the directing group of a complex
(serving as the solvent) and high temperature of the syn- structure.
thesis. Scheme 38
Scheme 36 Directing group X
Directing I
group O
N O N
O OR O
R1 R2OH, Cu(OAc)2, R1 Pd(OAc)2 (cat.)
N AgOTf, O2 N N ROH or N
140 8C, 24 h H ROH is xylene H
OR2
(32% ± 82%) X = OMe, OAc
R2 = Et, Bun, Pri, CH2All, CH2Bn, (CH2)2OMe, etc. Related acetoxylation of alkyl and aryl CH fragments of
Ph Ph O-acetyl oximes is induced by the Pd(OAc)27PhI(OAc)2
BunOH, Cu(OAc)2, system in an AcOH ± Ac2O mixture (Scheme 39).160 The
AgOTf, O2 BunO acylation of the oxime and CH-acetoxylation are conducted
N 140 8C, 24 h N
(57%) Scheme 39
HO
R1 N
AcOH7Ac2O (1 : 1)
N
258C, 2 h
CuIII
Directing
R2O X
group
Presumed intermediate
AcO AcO
N Pd(OAc)2 (5 mol.%), N OAc
Some reactions of arene acetoxylation and alkoxylation PhI(OAc)2 (1 ± 3 equiv.)
are catalyzed by Pd(OAc)2 , suitable oxidants include 80 ± 100 8C, 4 ± 12 h
K2S2O8 , potassium peroxymonosulfate (oxone, (`one pot')
KHSO5 . 0.5 KHSO4 . 0.5 K2SO4), PhI(OAc)2, and an (33%786%)
oxime, amide, N-alkoxyamide, nitrile or azo moiety can Examples of obtained products
serve as the directing group. For example, oxidative cou- (in parentheses are the yields)
pling of anilides with alcohols has been performed under the
OAc O
action of the Pd(OAc)27MeSO3H7K2S2O8 system
N OAc
5
Scheme 37 N N
Directing OAc
group (61%) O OAc
O (65%)
O
ROH (510 equiv.), Pd(OAc)2, OAc OAc
NH NH OAc N N
K2S2O8, MeSO3H
H
MeO(CH2)2OMe, 25 8C, 24 h Br
OR
(36% ± 77%) OAc
H
R = n-Alk, cyclo-Alk, (CH2)2Cl, (CH2)2OMe (86%)
(41%)
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 901
O
a =
R1 = Ar, Het, 4-ClC6H4CH CH, PhCH CBr, But; =
OH
+
O
R27R3 = CH2CH2, o-phenylene; R4 = Ar, PhCH CBr; =
(a) Bun4 NI (10 mol.%) or Bun4 NBr (10 mol.%),
(1 equiv.) (4 equiv.)
ButOOH (5.5 M decane solution) (2 equiv); EtOAc, 70 8C, 7 ± 12 h;
O
(b) Bun4 NI (10 mol.%), ButOOH (5.5 M decane solution) (2 equiv.),
(a) Bun4 NI (20 mol.%), ButOOH (70% aq.) (1.5 equiv.), PhH, 80 8C, 8 h EtOAc, 70 8C, 6 h
Examples of obtained products The Bun4 NI7ButOOH system can also serve for the
oxidative coupling of aldehydes with ButOOH (Scheme 44).
O Y = 2-MeC6H4 (89%), cyclo-C3H5 (79%), The tert-butyl peroxy esters thus formed find use in the
CH2Bn (80%), CH2NHBoc (67%) functionalization of the allylic position of alkenes to give
Y O
O Z = Bn (23%), thNaph (85%), Scheme 44
Z
O =
CH2C(Me) CPh2 (98%), O
Bun4 NI (20 mol.%) O
=
CH2CH C6H10-cyclo (72%)
R H
+ ButOOH
H2O (2 ml), 40 8C, 24 h R O
O
But
Cl (thNaph is 1,2,3,4-tetrahydro-1-
(0.5 mmol) (1.5 mmol) (43% ± 92%)
naphthyl)
R = Ar, Cy
The Bun4 NI7ButOOH system proved to be also efficient O
.
in the oxidative C7O coupling of ethers with carboxylic O Bun4 NI (20 mol.%),
acids (Scheme 42).164 The coupling was carried out with H N ButOOH (3 equiv.)
+
low-molecular-mass ethers taken in a 20-fold excess with H2O (2 ml), 40 8C, 24 h
respect to the acid. It is assumed that the tert-butoxyl
radical generated in the Bun4 NI7ButOOH system detaches O
a hydrogen atom from the a-position of the ether; the N
C-radical thus formed is oxidized to the carbocation, O
which reacts with the carboxylate anion to give the coupling
product. (99%)
902 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
allylic esters by the Kharasch ± Sosnovsky reaction.166 Pre- carboxylic acid (O-component).168 2,3-Dichloro-5,6-
sumably, tert-butylperoxy esters are formed upon recombi- dicyano-1,4-benzoquinone is used in some other oxidative
nation of acyl and tert-butylperoxyl radicals (Scheme 45). C7O coupling reactions involving alcohols, phenols, thiols,
The radical reaction mechanism is confirmed by the carboxylic acids 168 and oximes as nucleophilic O-compo-
experiment in which the acyl radicals were trapped by =
nents and ArCH CHCH2R or ArC:CCH2 R with the
TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl radical) activated allylic or propargylic position as C-components.
(see Scheme 44). Using the Cu(OAc)27ButOOH system, oxidative C7O
Scheme 45 coupling of aldehydes with alkylarenes was performed
. (Scheme 47).169 A specific feature of this coupling is the
ButOOH ButO + HO7
formation of two C7O bonds and cleavage of two C7H
bonds; the same type of coupling of methyl- and ethylarenes
I7 0.5 I2 with aromatic aldehydes was accomplished on treatment
with the Bun4 NI7ButOOH system using an excess of either
. alkylarene or aldehyde.170
H2O + ButOO ButOOH + HO7
Scheme 47
O . O . O
ButO ButOO
O R3
. O Cu(OAc)2 . 2 H2O (0.1 mmol),
R H R R O But ButOOH (2 mmol)
+ R2
R1 100 8C, 1.5 ± 7 h
Yet another class of C-components used in the oxidative
C7O coupling are alkylarenes. Under the action of the (1 mmol) (2 mmol)
Pd(OAc)27CF3SO3H7DMA7O2 system (DMA is dime- O R3
thylacetamide), benzylation of aryl-, alkyl- and cycloalkyl-
carboxylic acids takes place; the reaction is carried out in R1 O
R2
toluene (Scheme 46).167 Probably, the process occurs by an
ionic mechanism in which the toluene C7H bond is cleaved (60% ± 88%)
under the action of PdII. The product is formed either upon
R1 = Ar, 2-Th, PhCH=CH, Cy; R2 = Me, Cl; R3 = H, Me;
nucleophilic attack of the PdII complex by the carboxylic
Th is thienyl
acid or upon reductive elimination (see Scheme 46). Pre-
sumably, the role of dimethylacetamide is reduced to
promotion of Pd0 reoxidation to PdII with oxygen and The oxidative C7O coupling of alkylarenes and related
suppression of Pd0 aggregation, while trifluorometanesul- compounds with N-hydroxyphthalimide was carried out
fonic acid facilitates the C7H bond cleavage in toluene via with the CuCl7PhI(OAc)2 (Ref. 171) or (NH4)2Ce(NO3)6
the formation of PdII cationic compounds.167 (Ref. 172) oxidants (Scheme 48). The CuCl7PhI(OAc)2
Scheme 46 system provides somewhat higher yields of coupling prod-
Pd(OAc)2 (10 mol.%), ucts than (NH4)2Ce(NO3)6 but requires higher temperature
CF3SO3H (10 mol.%), and longer duration of the synthesis. Apparently, the C7O
O
DMA (0.5 mmol),
O Ph bond is formed upon recombination of benzyl and phthali-
O2 (1 atm) mide-N-oxyl radicals, while side recombination of the
+
R OH 115 8C, 24 h R O benzyl radicals with each other and oxidation of benzyl
(0.5 mmol) (0.5 ml) (64% ± 92%) radicals to give alcohols and carbonyl compounds can be
avoided; however, for attaining high yields, alkylarenes are
taken in excess. Coupling of N-hydroxyphthalimide with
R = Ar, PhCH =CH, 4-FC H CH , n-C H
6 4 2 7 15, cyclo-C3H5, Cy
ethers and alkenes proceeds in a similar way.171
Possible ways of C7O bond formation Scheme 48
O
PdII
a or b
O + HO N
R OH O Ph O
RCOO PdII + Pd0 O
R O
O N
O
The oxidative coupling of diarylmetthanes with carbox-
ylic acids is induced by MnO2 in the presence of a catalytic (a) CuCl7PhI(OAc)2, 70 8C, 12 h;
amount of DDQ. It is assumed that DDQ oxidizes diaryl- (b) (NH4)2Ce(NO3)6, 20 ± 25 8C, 30 min
methanes to diarylmethyl cations, which react with carbox-
ylic acids to give esters. Manganese dioxide serves for Most of oxidative C7O coupling reactions involving
oxidation of the reduced form of the catalyst to DDQ. A the a-position of carbonyl compounds utilize iodo-contain-
drawback of the method is that it requires the presence of ing oxidants. Most often, organic compounds of iodine(III)
two aryl moieties at the reaction centre of the C-component are used, including those generated in situ from aryl iodides
of coupling and the use of a four-fold excess of the and carboxylic peroxyacids such as m-chloroperoxybenzoic
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 903
and peroxyacetic acids. These processes follow an ionic retained unchanged. The reaction is assumed to follow a
mechanism: the electrophilic iodine atom attacks the enol radical mechanism.174
derived from the dicarbonyl compound; then the O-nucleo- N-Hydroxyimides and N-hydroxyamides enter into the
phile replaces the iodine-containing group to give the C7O- oxidative C7O coupling with 1,3-dicarbonyl compounds
coupling product (Scheme 49). and their heteroanalogues, 2-substituted malononitriles and
Scheme 49 ethyl cyanoacetates, under the action of manganese-,
.. cobalt- and cerium-based oxidants.175 The best results
.. ROH
OH O .. were obtained with Mn(OAc)3 and the Co(OAc)2(cat.)7
..
O O
KMnO4 system; the product yields are up to 94% without
the need of using excesses of reactants (Scheme 52). The
OR 7XH, 74-MeC6H4I formation of imide-N-oxyl radicals during oxidative cou-
I
I X (X = OR, OH) pling was detected by EPR spectroscopy. Presumably, the
X oxidizing metal performs two functions: generation of the
N-oxyl radicals from N-hydroxyimides or N-hydroxyamides
O O and one-electron oxidation of 1,3-dicarbonyl compounds.
Scheme 52
OR EWG1 EWG2
Mn(OAc)3 or EWG1 EWG2
H Co(OAc)2 (cat),
Indeed, p-(difluoroiodo)toluene induces the oxidative cou- KMnO4 O
pling of b-dicarbonyl compounds with various OH-re- O H AcOH, 60 ± 80 8C,
10 min O N
agents: sulfonic and carboxylic acids, diphenyl hydrogen O
phosphate and alcohols (Scheme 50).173 N
Scheme 50 (30% ± 94%)
O O EWG1, EWG2 = CO2Et, Ac, CN
O O
Recently, oxidative coupling of 1,3-dicarbonyl com-
pounds with oximes, which apparently follows a similar
OAlk
mechanism, was documented (Scheme 53).176 The reaction
is induced by the oxidants KMnO4 , Mn(OAc)27KMnO4 ,
(a) RSO3H (R = Me, 4-MeC6H4), 5 ± 30 min; (b) (PhO)2P(O)OH, Mn(OAc)3 . 2 H2O, MnO2 , Mn(acac)3 (acac is acetylaceto-
15 ± 20 min; (c) AcOH, 15 ± 80 min; (d ) AlkOH (Alk = Me, Et, Pri), nate), Fe(ClO4)3 , Cu(ClO4)2 . 6 H2O, Cu(NO3)2 . 2.5 H2O or
0.5 ± 24 h (NH4)2 Ce(NO3)6 . Using KMnO4 , Mn(OAc)3 . 2 H2O or the
phosphine complexes.194 A considerable part of synthetic oxide requires thorough purification of this PV7H sub-
procedures published later also used various Pd phosphine strate. Unfortunately, the researchers did not describe the
complexes as catalysts and provided branched alkenyl- purification of Ph2P(O)H before the reaction.
phosphonates (a-isomers).195 ± 197 Subsequently, the [Ni]7Ph2P(O)OH catalytic system
Successful use of rhodium complexes for catalytic was used in the reaction of propargyl alcohols with various
hydrophosphorylation of alkynes giving selectively only PV7H substrates [H-phosphonates, H-phosphinates and
the linear b-E-isomer was demonstrated for some examples. Ph2P(O)H], which made it possible to obtain phosphinoyl-
This difference of the selectivity of addition in the presence 1,3-dienes in high yields (Schemes 57 and 58).202
of complexes of different metals (Pd and Rh) was attributed Scheme 57
to differences at the step of alkyne insertion, which involves R
the Pd7P bond in one case and the Rh7H bond in the [Ni]7Ph2P(O)OH
[P]7H +
other case. However, in both cases, the reaction proceeds as R
OH
7H2O (`one-pot')
syn-addition. Thus, Pd- and Rh-catalyzed hydrophosphor- [P]
ylations of alkynes supplement each other, thus enabling the
(57% ± 99%)
selective synthesis of isomeric a- and b-E-alkenylphospho-
nates, respectively.198, 199 [P]7H = (MeO)2P(O)H, Ph2P(O)H, Ph(EtO)P(O)H;
A recently developed procedure allows controlling the R = Me, Ph, 4-MeC6H4, 4-MeOC6H4, 4-Me2NC6H4, etc.
selectivity of Pd-catalyzed reaction, which can be used to
synthesize both branched (a-) and linear (b-E-) products.200 Scheme 58
The control of the selectivity was achieved by deliberate Ni(PPhMe2)4 (5 mol.%),
modification of the coordination sphere of palladium inter- Ph2P(O)OH (10 mol.%)
+ (MeO)2P(O)H
mediates by choosing the appropriate ligand out of the OH THF, 20 8C, 16 h, 7H2O
series P{(MeO)nC6H57n}3 .200 This approach to the regiose-
lectivity control has no analogues among reactions of this
type. P(O)(OMe)2 +
P(O)(OMe)2
In 2004, a study of alkyne hydrophosphorylation cata-
(68%, a : b = 77 : 23)
lyzed by nickel complexes was published,201 being con-
cerned with the effect of diphenylphosphinic acid
[Ph2P(O)OH] on the reaction regioselectivity with the use A more detailed comparative analysis of published data
of Ni systems with different phosphorus ligands (see Schemes 56 and 58) 201, 202 discloses some contradic-
(Scheme 56). Unfortunately, in this case, it is impossible to tions in the presented results and brings about some ques-
identify the key factor responsible for the regioselectivity of tions. Indeed, earlier the same authors demonstrated 201 the
addition, because the reactions were carried out in different possibility of hydrophosphorylation of oct-1-yne with dime-
solvents (THF, ethanol) with addition of the acid [Ph2 thylphosphite on a nickel catalyst (see Scheme 56); how-
P(O)OH] and without the acid using various catalyst pre- ever, only 1 mol.% of the nickel-containing catalyst
cursors and ligands of various nature (PPh2Me and precursor was used, whereas in the reaction of dimethyl
PPhMe2) (see Scheme 56).201 The authors also did not phosphite with 2-methylbut-3-yn-2- ol (see Scheme 58), the
present the interpretation of the regioselectivity change amount of the catalyst precursor was 5 mol.%.
from the standpoint of the reaction mechanism. In addition, in the latter case, the reaction was carried
Scheme 56 out for 16 h rather than for 2 h as the reaction with oct-
1-yne. It can hardly be conceived that the presence of the
n-H13C6 + (MeO)2P(O)H
hydroxy group in the aliphatic moiety at the triple bond can
n-H13C6 have so adverse effect on the addition reactions and can
Ni(PPh2Me)4 (0.5 mol.%) require a 5 times greater amount of the catalyst for a 8 times
EtOH, 20 8C, 5 h P(O)(OMe)2 longer reaction time. One more fact is noteworthy, in
(96%, a : b = 7 : 93) particular, in this synthetic procedure, the authors use
Ni(cod)2 (1 mol.%), 10 mol.% Ph2P(O)OH (see Scheme 58) instead of 2 mol.%
PPhMe2 (4 mol.%), used earlier (see Scheme 56) but the product yield was much
n-H13C6
Ph2P(O)OH (2 mol.%) lower in this case: 68% and 91%, respectively. Note that in
THF, 20 8C, 2 h the presence of 10 mol.% Ph2P(O)OH, the regioselectivity
(MeO)2(O)P
is lower: the content of the a-isomer is only 77%, while in
(91%, a : b = 92 : 8) the presence of 2 mol.% Ph2P(O)OH, it is 92% (see
Schemes 56 and 58).201, 202 The use of different amounts of
Note that a similar effect of the Ph2P(O)OH additive the catalyst precursor and contradictory data on the effect
was also observed for the Ni-catalyzed addition to alkynes of acid addition on the regioselectivity with the alkyne
of other PV7H substrates Ð Ph(EtO)P(O)H and structure being varied preclude drawing unambiguous con-
Ph2P(O)H.201 However, in these cases, too, the factor clusions about the general applicability of the
responsible for the control of regioselectivity remained [Ni]7PPhMe27Ph2P(O)OH system proposed by the
unidentified for the above-indicated reasons. Moreover, authors to hydrophosphorylation of terminal alkynes.
commercially available diphenylphosphine oxide A procedure of alkyne hydrophosphorylation using
[Ph2P(O)H] used by the researchers 201 contains, as a rule, inexpensive and oxygen- and air moisture-stable Ni(acac)2
a noticeable amount of the acid Ph2P(O)OH formed upon as the catalyst precursor was developed in 2010.203 With this
oxidation. Therefore, study of the effect of the acid on nickel complex, the catalytic reaction can be carried out
alkyne hydrophosphinylation with diphenylphosphine without addition of the acid with no decrease in the yield or
906 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
selectivity. The addition of H-phosphonates with various and (EtO)2P(O)H 208] was performed to give a- and
substituents to terminal and internal alkynes was accom- b-adducts and cyclic vinylphosphonate derivatives.
plished with high regio- and stereoselectivity (Scheme 59).
Scheme 61
Scheme 59
R1 R2 + (R3O)2P(O)H
Ni(acac)2 (9 mol.%), R1 R2
[Ni] (9 mol.%)
dppe (18 mol.%) R1 R2
R1 R2 + (R3O)2P(O)H (99%) P(O)(OR3)2
THF, 100 ± 140 8C,
20 ± 30 h (R3O)2(O)P R1 = R2 = Ph, Et;
R1 = Ph, R2 = Me
(61% ± 99%) Ni(acac)27DIBAL
R1 = R2 = Ph, Et; R2 = H: R1 = n-C5H11, NC(CH2)3, Ph;
R3 = Pri, n-C12H25, Bn, Ph; R37R3 = CH(Me)CH(Me); R1 R2
dppe = Ph2P(CH2)2PPh2
[Ni] (1 mol.%)
(R3O)2(O)P P(O)(OR3)2
(99%)
The mechanism of catalytic hydrophosphorylation of
R1 = R2 = H, Ph;
alkynes was examined using quantum chemical calcula- R3 = Pri, n-C12H25, Ph R2 = H: R1 = n-C5H11, Ph
tions.204 Comparative analysis was done for the two alter-
native pathways of alkyne insertion either at the
metal7phosphorus bond or at the metal7hydrogen bond. The moderate number of publications is due to low
It was demonstrated for the first time that alkyne can be reactivity of diynes in hydrophosphorylation. The
inserted much more readily into the M7H bond than into Ni(acac)27dppe-based catalyst, which showed high effi-
the M7P bond. The same publication 204 demonstrated that ciency in the hydrophosphorylation of hept-1-yne,203
the catalytic hydrophosphorylation of internal alkynes can, proved to be inefficient for hepta-1,6-diyne.209 Evidently,
in principle, occur without a phosphine ligand. the substantially lower reactivity of diynes compared to
Yet another vivid example of nickel-catalyzed hydro- alkynes is due to the presence of the second triple bond in
phosphorylation is the addition of H-phosphonates to the molecule; however, the cause of this unexpected phe-
ynamides.205 The best result was achieved with NiBr2 nomenon is still unclear.
(10 mol.%) (Scheme 60). In 2013, hydrophosphorylation of a number of diynes
Scheme 60 was accomplished in the presence of a nickel catalyst.209 The
Ts NiBr2 (10 mol.%) Ni(acac)27DIBAL catalytic system described above 207
N Ph + (RO)2P(O)H provided the formation of alkyltetraphosphonates 21 upon
PhMe
Bn the addition of H-phosphonates of different nature to
P(O)(OR)2
diynes. The products were obtained in good (up to 91%)
Ts
N Ph yields. This work was the first example of the synthesis of
alkyltetraphosphonates by the catalytic reaction of H-phos-
Bn (35% ± 97%) phonates with diynes.209
R = Me, Et, Pri Structures 21
RO OR
P P
The current trend of going from palladium to nickel RO OR
catalysts is attributable, first of all, to the economic factor, P P
O
RO O RO OO
i.e., high cost of palladium compounds. Also, some organic OR OR
nickel derivatives [for example, Ni(acac)2] are attractive 21
from the practical standpoint, as they are air stable, can be R = Et, Pri, Ph
stored for long without the loss of activity, whereas some
palladium compounds have low stability even in the solid V.1.b. The addition of secondary phosphine oxides R2P(O)H
state [for example, Pd2(dba)3, dba is dibenzylideneace- (hydrophosphinylation)
tone].206 As in the case of hydrophosphorylation, studies of the
Recently, high catalytic activity of the system catalytic hydrophosphinylation of acetylene hydrocarbons
Ni(acac)27DIBAL (DIBAL = Bui2 AlH) in the hydrophos- were started in the second half of the 1990s. The develop-
phorylation of terminal and internal alkynes was found and ment of both reactions was pursued in parallel, both similar
explored.207 The hydrophosphorylation proceeds without a and distinctive features being revealed in the course of
solvent and does not require the use of phosphine ligands or studies.
acid additives. The Ni(acac)27DIBAL system provides a Commercially available H-phosphonates are repre-
unique possibility for controlling the selectivity by changing sented by a series of inexpensive compounds, while the
the amount of Ni(acac)2 (1 mol.% or 9 mol.%): either marketed secondary phosphine oxides are limited to only a
mono- or 1,2-bis-phosphonate can be obtained in a quanti- few expensive PV7H substrates of this class. Among these,
tative yield (Scheme 61). diphenylphosphine oxide has the lowest cost, but still it is
To date, only a few publications have been devoted to tens and sometimes hundreds times more expensive than
the catalytic hydrophosphorylation of diynes.194, 198, 208 In H-phosphonates. Furthermore, as has already been noted,
the presence of palladium 194, 208 and rhodium 198 catalysts, commercial Ph2P(O)H contains, most often, noticeable
addition of simple aliphatic H-phosphonates quantities of the acid Ph2P(O)OH; therefore, thorough
[(MeO)2P(O)H,194, 208 (cyclo-OCMe2CMe2OP)(O)H 198, 208 preliminary purification of this reagent is required, which
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 907
increases the duration and the cost of the whole synthetic diphenylphosphine oxide in the presence of Pd(PPh3)4 217 or
procedure. Nevertheless, there are several examples of binuclear or trinuclear Pd7M catalysts (M = Ti, Zr, Hf);
reported catalytic addition reactions of commercial the process occurs under mild conditions (40 8C, 1 h) and
Ph2P(O)H to acetylene hydrocarbons.201, 202, 210 ± 215 Com- gives products in high yields (>95%).218
plexes of various metals (Pd, Rh, Ni, Cu) were used as A recent paper 215 describes the procedure of addition of
catalysts. Analysis of published data shows that many chiral enantiomerically pure 1r-oxo-2c,5t-diphenylphospho-
characteristic features of hydrophosphorylation reactions lane to terminal alkynes catalyzed by Pd and Rh complexes.
are also observed for hydrophosphinylation. The use of The selective formation of a- and b-E-isomers in Pd- and
nickel catalysts for this class of reactions was discussed Rh-catalyzed reactions, respectively, was demonstrated
above.201, 202 (Scheme 64). Unfortunately, although the product yield
It was shown that the Rh complex-catalyzed addition of calculated from NMR data was often higher than 95%,
Ph2P(O)H to alkynes can proceed without a solvent under most products were isolated in yields of about 25% ± 40%,
microwave irradiation (MW),213 the reaction time in this which was attributed by the authors 215 to destruction of the
case being decreased to several minutes. This reaction, like alkenylphosphine oxides on silica gel during chromatogra-
all the processes involving Rh complexes discussed above, phy.
gave, with high selectivity, linear b-(E )-alkenylphosphine Scheme 64
oxides (for terminal alkynes) and syn-addition products (for
internal alkynes). The possibility of microwave-assisted bis- O
Ph
hydrophosphinylation with 2 ± 3 equivalents of Ph2P(O)H R
P
was demonstrated 213 (Scheme 62). [Pd]
Scheme 62 Ph
Ph
PhMe, 80 8C, a (>95%)
Ph2(O)P P(O)Ph2 O
R 15 h
P + R
40 min O
[Rh]
R H Ph R
Ph2P(O)H P
no solvent, MW Ph [Rh]
(2 ± 3 equiv.) Ph2(O)P P(O)Ph2
R1 R2 (R,R) Ph
20 min R1 R2 b (57% ± >95%)
[Pd] = Pd(PPh3)4, [Rh] = [Rh(cod)Cl]2
The same study reports the possibility of using polymer-
supported catalysts, which provides regeneration and reuse The ratio between two alternative processes, namely,
of the metal complex.213 This approach to the design of a regioselective addition to give the a-isomer and bis-hydro-
catalytic system, i.e., the use of microwave radiation, phosphinylation, in the reaction of terminal alkynes with
catalyst recycling and the absence of solvent, is consistent Ph2P(O)H catalyzed by Pd complexes was studied.219 In the
with the green chemistry requirements and makes it possible presence of the bidentate dppe ligand, branched a-adducts
to decrease the expenditures for the synthesis. were formed in good yields (64% ± 88%) and with high
Yet another important transformation catalyzed by Rh selectivity (95% ± 99%). When a monodentate ligand was
complexes is the addition of Ph2P(O)H to the triple bond of used [P(o-Tol)2Ph, o-Tol is o-tolyl], bis-hydrophosphinyla-
ethynylsteroids Ð microwave-assisted hydrophosphinyla- tion occurred predominantly to give a reasonable yield
tion insensitive to air oxygen and moisture.216 The reaction (48%) of the corresponding product.
occurs in water as the solvent and affords a linear In 2007, alkyne hydrophosphinylation was implemented
(b-E-isomer) addition product in good yield (Scheme 63). in the presence of the CuI71,2-diaminoethane system
The use of water is highly untypical for the addition of (Scheme 65).220 The use of Ph2P(O)H and Bn2P(O)H as
molecules with a PV7H bond to alkynes; as a rule, these the PV7H substrates resulted in the formation of b-alke-
transformations are adversely sensitive to even traces of nylphosphine oxides in good yields and with high stereo-
water. selectivity.220
Scheme 63 Scheme 65
OH
n-H13C6
CuI (10 mol.%) R
[Rh], H2O n-H13C6 + R2P(O)H
H2N(CH2)2NH2 (15 mol.%), P
Ph2P(O)H +
MW DMSO, 90 8C, 12 ± 18 h
O R
O OH (R = Ph, 67%; E : Z = 85 : 15;
P(O)Ph2 R = Bn, 72%; E : Z > 99)
Scheme 66 Scheme 68
Ph O
P Pd(OAc)2 (5 mol.%),
O (5 mol.%)7L dppe (7.5 mol.%)
Ph + (EtO)PhP(O)H
Pd PhMe, 100 8C, 3 h
(22)
R1 + R22 P(O)H
PhMe Ph Ph
+
R1 R1
(EtO)Ph(O)P P(O)Ph(OEt)
+
a (89%) b
R22 (O)P P(O)R22
a b
In 2013, Montchamp and co-workers 232 published a
R1 R2 L T /8C Time /h Yield (%) a : b study devoted to Pd-catalyzed reactions of phosphorus7
carbon bond formation. By using the Pd(OAc)27dppf
n-C6H13 Ph dppp 70 3 99 98 : 2 system as the catalyst [dppf is 1,10 -bis(diphenylphosphino)-
n-C6H13 Me dppp 110 5 99 98 : 2 ferrocene], the addition of various H-phosphinates to inter-
But MeO dppe 110 25 95 98 : 2 nal oct-4-yne was accomplished.
But see a dppe 70 19 97 99 : 1 Thus, the addition of PV7H substrates to the triple
carbon ± carbon bond is of obvious interest as a tool of
a R27R2 = O(CMe2)2O; dppp = Ph2P(CH2)3PPh2. hydroheterofunctionalization of organic compounds and
opens up broad prospects for the development of effective
procedures for the synthesis of valuable C7PV derivatives.
The use of the catalytic system CpPd(Z3-All) ± dppben ± The variation of substituents in one or both reactants
[3,5-(CF3)2C6H3]2P(O)OH [Cp = Z5-C5H5, dppben = 1,2- (PV7H-substrate and alkyne) may furnish adducts with a
(PPh 2 ) 2 C 6 H 4 ] resulted in the addition of dibutylphos- specified structure and properties (polarity, solubility, melt-
phine oxide to some terminal alkynes and diphenylace- ing and boiling points). The C7PV derivatives of various
tylene. 222 organic compounds find use in important areas of human
activity.
V.1.c. The addition of hypophosphites (RO)P(O)H2 and Despite the achievements (see above), many problems in
H-phosphinates (RO)(R0 )P(O)H (hydrophosphonylation) this field of chemistry still remain unsolved. These include:
The number of reactions of this class reported in the (i) the absence of microwave-assisted synthetic procedures
literature is much less compared to those for hydrophos- and catalyst recycling methods for catalytic hydrophos-
phorylation and hydrophosphinylation. Effective catalytic phorylations; (ii) rather limited number of substrates for
systems based on palladium ([Pd] is phosphine ligand) for some reactions; (iii) unexpectedly low reactivity of diynes
selective addition of hypophosphites to acetylenic hydro- and, as a consequence, few examples of catalytic reactions
carbons are known.223 ± 227 The use of catalytic amounts of involving them; (iv) contradictory data obtained for reac-
NiCl2 provided the addition of alkylphosphinates to termi- tion mechanisms; and (v) the absence of procedures for
nal and internal alkynes without a phosphine ligand.228 conducting these reactions in `green' solvents such as poly-
Unfortunately, in the case of NiCl2, the reaction regioselec- ethylene glycols, ionic liquids or supercritical media.
tivity was lower than in a similar process involving Pd
complexes, and hydrophosphonylation of terminal alkynes VI. N-Heterocyclic carbene ligands in
led to a mixture of a- and b-isomers.
In 2007, a two-step procedure for the synthesis of
homogeneous catalysis
various phosphonic acids was developed.229 The first step From the previous Sections, it is obvious that appropriate
was the addition of hypophosphorous acid [HOP(O)H2] to selection of the catalyst plays the key role in the control of
the alkyne triple bond to give alkenyl-H-phosphinate the reaction route and for attaining high selectivity. It is the
(Scheme 67). In the second step, the product was oxidized appearance of new ligands that predetermined the success of
with air oxygen in dimethylformamide, which gave rise to homogeneous metal complex catalysis in this field of chem-
the corresponding phosphonic acid. istry. This can be exemplified by the use of stable N-hetero-
Scheme 67 cyclic carbenes (NHC) as ligands in catalysis.
In the last 20 years, the chemistry of stable carbenes has
O
been an actively developing line of research at the boundary
O
H Pd2(dba)37Xantphos
R2 P OH of organic and organometallic chemistry and homogeneous
HO P + R1 R2 H catalysis. In 1991, Arduengo et al.233 demonstrated in
DMF, N2, 85 8C
H R1 relation to compound 23 that free carbenes can be isolated
in a pure state. This work aroused considerable interest and
attracted new research teams into this area. Effective
In the small number of examples of H-phosphinate methods for the synthesis of free carbenes of various
addition to alkynes, phenyl-H-phosphinates were used in types 234, 235 and carbene complexes with transition met-
all cases as the P V 7H substrates. 201, 202, 220, 221, 230 It was als 236 ± 240 were developed. Free carbenes are now widely
found that an acceptable selectivity of a-isomer formation used as organocatalysts.241 ± 244 Carbene complexes with
in the Pd-catalyzed reaction can be achieved without transition metals serve as the basis for effective catalytic
the addition of acid. 231 Good results were attained by systems for C7C and C7N cross-coupling reactions,
using the Pd(OAc)2 7dppe system as the catalyst alkene metathesis (see Section III) and some other impor-
(Scheme 68). 231 tant catalytic processes.245 ± 250
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 909
N N N N N N N N N N N N N
7 N 7 .. .. .. ..
+ +
..
..
..
..
..
N N 32 33 34 35
N N R
24 25 26 27 28 O O O O7 O O
N N N N N N
N .. .. ..
36 37 38
N 7 N
+
..
..
..
N n
N n = 1 (a), 2 (b), Owing to their heterocyclic nature, carbene ligands can
N 3 (c) be modified and functionalized in a variety of ways. Indeed,
30 31a ± c
29 carbenes (or carbene complexes) based on chiral polyhe-
teroaromatic structures (carbene 39) 268 and natural phys-
As compared with five-membered analogues, expanded iologically active derivatives (40 and 41) 269 have been
ring carbenes have a number of specific features that make synthesized. Mention should be made of unusual carbene
them potentially suitable for the design of catalysts: 42 containing a ferrocenyl moiety.270 A number of triden-
Ð higher donor ability; tate ligands containing imine (43),271, 272 phosphine (44) 273
Ð the possibility to vary the steric crowding of the or pyridine (45) 274 groups as the coordinating moieties have
ligands over wider limits; been developed on the basis of six-membered ring diamino-
Ð higher energy of the metal7ligand bond; carbenes.
Ð higher thermal and hydrolytic stability of the com- Structures 39 ± 45
plexes and stability against oxidation.
The present Section of the review considers examples of O O
using expanded ring carbene complexes in homogeneous N N
N N N
metal complex catalysis.
..
Ph
N N N N
..
..
N N
VI.1. Expanded ring diaminocarbenes and metal complexes ..
Ph
The first complexes of N-heterocyclic carbenes containing a 39 40 41
six-membered ring were obtained by Lappert's research
team back in 1977 253, 254 well before the isolation of free
N
carbenes. The reaction of tetraaminoethylenes with transi- N N
tion metal complexes is accompanied by C C bond = Fe ..
..
N N N N
cleavage to give new complexes (Scheme 69). The first free N ..
Ar Ar
diaminocarbene with a six-membered ring was isolated and 42 43 PR2 44 PR2
characterized by X-ray diffraction in the crystalline state in
2003,255 while carbenes with seven- 256 and eight-mem-
bered 257 rings were prepared and studied in 2008 and N N
2011, respectively. The methods of synthesis of carbenes ..
and their complexes have been considered in detail in a N 45 N
recent review.258 This Section briefly presents the structural
910 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
In order to modify the steric and electronic properties of from zwitter-ionic carboxylates (see Scheme 70, path-
carbenes, bicyclic diaminocarbenes have been prepared. The way e).295, 296 The complexes can be prepared by the
synthesis of carbene 46 based on a camphor derivative was oxidative addition of 2-haloamidines (see Scheme 70,
reported.275 ± 277 Bertrand and co-workers 278 proposed pathway f ) 297 and by cyclization of metal-coordinated
structure 47 in which one nitrogen atom occupies the isonitriles with g-chloro derivatives of secondary amines
bridgehead position. This carbene should be regarded as (Scheme 70, pathway g).298
monoamino- rather than a diaminocarbene, because the Scheme 70
electron pair of only one nitrogen atom is involved in
stabilization of the ylidene moiety. N
H . HCl
..
Structures 46, 47 n N Cl +
N R0
N +R N C M
a g
N n
AgHal
N N N b +
N
..
.. N N
f
47 M Hal
46 n n
+ c N N
N
The chemistry of carbenes containing seven- and eight- H e
n d
membered rings has been much less developed than the N
chemistry of six-membered ring carbenes. Diaminocarbenes
+
comprising an aliphatic moiety (31a),256 one (48) 256 or two N H N O7
(49) 279, 280 benzene rings, tricyclic (50) 281 or heterocyclic n n
N H N O
(51) 282 moieties have been described. The synthesis of
complexes of seven-membered ring diamidocarbene 52 has
been reported.283 There is only one example of diaminocar- M is transition metal, [M] is the metal compound, B is base,
bene 31c containing an eight-membered aliphatic ring.257 n = 1 ± 3; (a) [M]; (b) [M], 7AgHal; (c) MB, 7HB;
(d ) [M], 7H2; (e) [M], 7CO2; ( f ) [M]; (g) 7HCl
Structures 48 ± 52
Despite the considerable diversity of methods, a few
transition metal complexes of this type have been synthe-
sized to date. No complexes of titanium, vanadium or zinc
group metals have been reported. Only a few examples of
N N chromium group metal complexes are known.253, 254, 272, 299
N N .. N N
.. .. Researchers' attention has mainly been attracted by com-
48 49 50
plexes of heavy transition metals. About a dozen of works
on the chemistry of iron group metal complexes were
O O published. Most of all, ruthenium complexes and their
catalytic properties in alkene metathesis were investi-
O O gated.271, 272, 274, 300 ± 305 The greatest number of stud-
N N N N ies 255, 257, 260, 262 ± 267, 272, 275, 281, 283 are devoted to cobalt
.. .. group metal complexes. This is largely due to the fact that
51 52 rhodium and iridium carbonyl complexes serve as conven-
ient models for investigation of the donor properties of
Transition metal complexes of N-heterocyclic expanded carbenes. For these complexes, the Tolman electronic
ring carbenes can be synthesized in several ways. Histor- parameter was calculated from the carbonyl vibrational
ically, the first developed approach Ð the Lappert method frequencies.306 On the increase in the donor capacity of the
(see Scheme 69) Ð includes the reaction of tetraamino- ligands (phosphines, carbenes, etc.), the carbonyl vibra-
ethylenes with a metal complex. The most facile and often tional frequency decreases. The decrease in the Tolman
an effective method for the synthesis of the complexes is the parameter corresponds to the increase in the donor proper-
direct reaction of free carbene with a metal salt (Scheme 70, ties of the ligand. Considerable attention of researchers was
pathway a). The free carbene can be either preliminarily devoted to the chemistry of nickel 270, 275, 279, 280, 284 ± 286 and
isolated (Refs 255, 267, 278, 283 ± 288) or generated in situ copper 268, 272, 275, 280, 283, 287 group metal complexes.
by treatment with an appropriate strong base
(Refs 259 ± 261, 264, 265, 268, 269, 272, 275 ± 277, 279 ± VI.2. Catalysis of cross-coupling, hydrogenation,
282). Transmetallation (see Scheme 70, pathway b) of silver hydrosilylation, hydroboration, hydroamination, arylation,
complexes 288 ± 290 or complexes of other metals (copper,291 polymerization and asymmetric reactions
palladium 280) is often used. A popular method is the VI.2.a. Suzuki reaction
reaction of metal complexes containing basic ligands with Suzuki reaction is the cross-coupling of aryl halides with
amidinium salts (see Scheme 70, pathway c). The deproto- arylboronic acids (Scheme 71). For the discovery of this
nation of the amidinium salt and the coordination of the reaction, A Suzuki, together with E Negishi and R Heck,
resulting carbene to the metal atom occur simultane- were awarded the Nobel Prize in chemistry for 2010.307 This
ously.256, 257, 274, 277, 292 ± 294 Note also the syntheses by dou- reaction is most efficiently catalyzed by palladium com-
ble C7H activation of diaminomethane derivatives plexes containing highly electron ± donating, sterically
(see Scheme 70, pathway d ) 273 and elimination of CO2 crowded 239 phosphine 308 or carbene ligands.309 The use of
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 911
expanded ring carbenes as ligands holds good prospects, Complexes based on carbenes containing five-, six- and
because they surpass both phosphines and five-membered seven-membered rings and bulky aromatic substituents
ring carbenes in the electron donor and steric properties.252 [Mes, 2,6-Pri2 C6H3 (Dipp)] were used. The complex com-
prising a six-membered ring carbene and the Dipp substitu-
Scheme 71 ent proved to be the most active catalyst. Using this
[Pd] catalyst, hetaryl chlorides of various nature can be coupled
X + B(OH)2 with boronic acids containing electron-donating, electron-
base
R R0 withdrawing or bulky substituents. The developed proce-
R0 dure complies with the green chemistry principles. The
following advantages of this procedure should be noted:
R (a) the reaction is carried out in water without adding
organic solvents; (b) the reaction is carried out in air with-
The first example of using palladium complexes with out solvent degassing; (c) a mild and cheap base, NaHCO3,
expanded ring carbenes in the Suzuki reaction was pub- is used; (d) small amounts of Bun4 NBr are needed; (e) a
lished in 2006 by Herrmann ad co-workers.310 Owing to the small excess of boronic acid is taken; (f) high yields are
high donor capacity of the carbene ligand, complex 53 is obtained after 1 h of refluxing; (g) high purity of the
very active in this reaction. The authors demonstrated that products containing no side homocoupling products is
in the presence of this catalyst, the reaction can involve both achieved. High activity of the catalyst is due to the appro-
deactivated aryl bromides and aryl chlorides. In the case of priate selection of the donor and steric properties of the
bromides, the process occurs efficiently in the presence of ligand. This resulted in the complex that exhibited high
0.005 mol.% palladium complex, the turnover number activity and was stable in the activated state in the reaction
being as high as 16106 in 14 h. For chlorides, these medium. It was also shown that these complexes efficiently
characteristics are 0.01 mol.% and 66103, respectively. catalyze the Suzuki reaction without a solvent.313
Subsequently, ligand 54 was employed to generate the
palladium complex in situ.311 High activity of the complex VI.2.b. Heck reaction
was demonstrated (turnover number of up to 1.876105, The Heck reaction is the coupling of alkyl and aryl halides
amount of the catalyst 0.005 mol.%) but the results were with alkenes catalyzed by palladium complexes
obtained only for highly active aryl iodides. (Scheme 72).314
It was shown 312 that on treatment with a base, salts 55 Scheme 72
and 56 form in situ palladium complexes, which catalyze the R
[Pd]
coupling of p-acetylchlorobenzene and phenylboronic acid, R X+ R0 base
giving products in almost quantitative yields within 2 h at R0
50 8C. However, it is noteworthy that large loads of
palladium salts and ligand precursors were used The first example of using expanded ring carbenes in the
(1.5 mol.% and 3.0 mol.%, respectively). Heck reaction was published in 2010.295 The reaction was
The synthesis of a series of palladium complexes based catalyzed by a palladium complex of a six-membered ring
on ferrocenyl diaminocarbene 57 was reported.270 The carbene chemically grafted to a polymeric resin. This
catalytic activity of the complexes was tested in the reac- catalyst showed a high activity in the coupling of styrene
tions of para-substituted aryl bromides with phenylboronic or n-butyl acrylate with aromatic bromides (turnover num-
acid. The complexes were found to give products in high ber of up to 16105). Homogeneous catalyst 59 demon-
yields with a catalyst amount of down to 161074 mol.%. strated a three times higher activity under similar
conditions.
Structures 53 ± 58 Structures 59, 60
Pri n
Cl N N N N N
N Pri Pri Ar Ar
N N
Pd Cl Cl Pd Cl Pd
N Pri Pri
PPh3 N+ +
N
Pri N N
Bun Bun Si Si
53 54 O
Y 59 60
Np Ar
N
X7 N N Ar = Mes, 2,6-Me2C6H3, 2-MeC6H4, 2-MeOC6H4; n = 1, 2
Ph
N+ Fe Pd
..
n
Ar N Complexes formed by benzyl-substituted carbenes 55
N Cl
55, 56 Ar and 56 catalyze the reactions of styrene with para-substi-
Np tuted phenyl bromides containing either electron-withdraw-
Y = Ar, X = Cl (55); 58 (n = 0 ± 2)
57 (Np is neopentyl)
Y = CH2OAlk, ing or electron-donating substituents to give products in
X = Br (56) >70% yields in 2 h.312 It was shown in 2011 that Pd0
complexes with six- and seven-membered ring carbenes
A publication of 2013 presents the results of a compa- (compound 60) catalyze the reaction of p-acetylbromoben-
rative study of the catalytic activity of palladium complexes zene with n-butyl acrylate.286 The product yields varied
58 in the Suzuki reaction of hetaryl halides in water.288 from 50% to 100% for the reaction time of 3 h depending
912 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
on the carbene ring size and the nature of aromatic Palladium complexes 60 (Ar = Mes, Dipp; n = 1, 2)
substituents at nitrogen atoms. The amounts of catalysts catalyze the reduction of alkynes with formic acid
used were low (0.1 mol.%). The complex containing ferro- (Scheme 74).318 It was found that at short reaction times,
cenyl ligand 57 demonstrated moderate activity in the cis-alkenes are predominantly formed. During 24 h, the
coupling of para-substituted aryl bromides with n-butyl reactions give alkanes almost quantitatively.
acrylate.270 Scheme 74
lowed by their oxidation to diols [reaction (3)] 324 occur in rhodium complexes but they increase the reaction selectivity
*80% yields. Noteworthy is the formation of chiral bimet- by reducing the trend of oxidation of alcohols to ketones.
allic boron and silicon derivatives [reaction (4)].325 In 2013, The same authors showed that a similar ionic rhodium
complex 70a was used for catalytic silylation of allyl complex containing the BFÿ 4 anion is more active than
phosphates with silylated pinacolborane Me2PhSi7BPin neutral complexes. In this case, the selectivity of the
[reaction (5)].326 catalytic reaction shifts towards the formation of keto-
Scheme 75 nes.294 In a similar reaction, rhodium complexes 62 with
B2Pin2, benzyl substituents (see Scheme 76) exhibit high activity
O BPin O and selectivity in the formation of alcohols, the yields
70a (1 mol.%)
(1) being 70% ± 95%.328
R OR R OR
(>88%, ee >82%)
B2Pin2 is bis(pinacol)diborane VI.2.i. Polymerization of phenylacetylene
A study of the catalytic activity of rhodium complexes
B2Pin2, BPin
62a ± d [R1 = R2 = Mes, n = 1, X = Cl (a), OTf (b), OBut
70b (1 mol.%) (2)
OAr (c), OC(O)CF3 (d)], 66a,b and iridium complexes 63
(>79%, ee >62%) [R1 = R2 = Mes, n = 1: X = Cl, OC(O)CF3] in the poly-
merization of phenylacetylene was reported.300 The polymer
OH 1) B2Pin2, OH thus formed (polyphenylacetylene, PPA) can have different
70b (1 mol.%)
O NO2 microstructures depending on the type of the catalyst used
2) H2O2
R R (3) (Scheme 77). All rhodium complexes showed a high cata-
OH lytic activity with predominant formation of the cis-isomer
(>81%, of PPA. In the case of catalysts 66a,b having ionic structure,
anti : syn > 95 : 5) the selectivity towards cis-PPA was 100%. The use of
B2Pin2, iridium complexes 63 resulted in the selective formation of
O NO2 70b (1 mol.%) BPin
M trans-PPA.
M (4)
Scheme 77
(>75%, ee >98%)
M = SiMe3, BPin
Me2PhSi7BPin, SiMe2Ph
70a (5.0 mol.%) Ph Ph
R1 OP(O)(OEt)2 (5)
R1
R2 Ph Ph Ph Ph
R2 Ph Ph
(25 ± 88%, ee >78%) trans
N
Ph
Ph
70a,b = N N [R = Me (a), But (b)]
Ph Ph
Cu Ph
R
Cl
Ph Ph Ph Ph
O R
Ph N 2) H3O+ n 7H2O
N O 80
O PG
N Ph
N N O 77
H
O O Ph n
Scheme 84 Scheme 87
R2 R3
R2 R3 n
R1 PPh3 [H]
N3 R1 PPh3 R1 R2
n N N
n
O 84 O X
85
n
R2 88 (62% ± 98%) (syn)
R1 N R2
79
R1 N R3
LiAlH4, Et3Al
79 (61% ± 92%) R1 R2
THF, 778 8C N
(n = 2)
R1 = Alk, Ar; R2, R3= H, Alk; n = 1, 2 X
89 (64% ± 91%) (anti )
Cl
93 = Ti Further, the method of biocatalyzed reduction of cyclic
Cl
imines 79 has recently started to be actively developed
(Scheme 95). The conversion can be as high as 99%, while
(R) the enantiomeric purity of the products is >99%.372 ± 376
The catalytic complex prepared from di-m-chlorobis(cy- VII.2.c. Friedel ± Crafts aminoalkylation (Mannich reaction)
cloocta-1,5-diene)diiridium(I) and (S,S)-f-BINAPHANE Alkylation of p-donor aromatic systems with imines is
(96) is an efficient catalyst for enantioselective hydrogena- classified in different papers as either Mannich reactions
tion of cyclic imines 79 suitable for preparing pyrrolidine or Friedel ± Crafts alkylation. The reaction between indoles
and piperidine derivatives 87 in high yields and with good 98 and cyclic ketimines 79 has recently been studied.378 It
enantioselectivity (Scheme 94).371 was shown that only perfluoroalkyl-substituted cyclic ket-
918 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
imines can participate in this reaction, while non-fluori- The addition of methylmagnesium bromide to imine 79g
nated analogues proved to be insufficiently electrophilic. was carried out in the presence of boron trifluoride ether-
The reaction is catalyzed by Lewis acids, the best results can ate.383 The desired compound 104 was isolated as a single
be achieved by using boron trifluoride etherate. Target diastereomer in high yields (Scheme 100).
compounds 99 were mainly formed in high yields Scheme 100
(Scheme 97). Ph Ph
Scheme 97
MeMgBr
P(O)(OEt)2
.
R2 P(O)(OEt)2 BF3 Et2O
N N
79g H
R2 104 (76%)
1) BF3 . Et2O R1 N
n 2) K2CO3, H2O
+ n Recently, a method for the synthesis of chiral amines
N RF was developed based on the reaction of imines with chiral
N RF
N
98 R1 79 H Lewis acid 105 to give iminium salts, which are then treated
99 (47% ± 87%) with an organometallic reagent (Scheme 101). For example,
upon the reaction with allylmagnesium bromide, complex
R1 = H, Me; R2 = Me, MeO; RF = CF3, C2F5; n = 1 ± 3 106 obtained from imine 79h was converted to optically
active pyrrolidine 107 in a high yield and with high
Perfluoroalkyl-substituted cyclic imines 79 can also enantiomeric excess.384
alkylate pyrroles 100 in the presence of boron trifluoride Scheme 101
etherate (Scheme 98). This reaction is characterized by But
unusual b-selectivity. Pyrrole reacts with five- and seven- N OTf
membered ring ketimines to give a- (101a) and b-substitu- B
+
tion (101b) products in *1 : 1 ratio. CF3-Piperideine alky- Fe
lates pyrrole only into the a-position. In the case of N
N-substituted pyrroles, electrophilic substitution at the 79h
b-position unusual for pyrroles is observed, which is due (7)-105
to thermodynamic control of the reaction.379, 380 It was
shown that other p-donor aromatic compounds cannot be But
alkylated by cyclic ketimines 79. N N
+
Scheme 98 B
1) MgBr Me
n BF3 . Et2O Fe
+ 2) B7N bond N
N F3C N cleavage
TfO7 SO2CF3
R 79
R 107 (96%, 94% ee )
100
R N 106
F3C n
N
N + n
H
F3C
VII.2.e. Mannich reaction
101a N
H In various publications, the reactions of imines with any of
101b
ketones, p-donor aromatic derivatives, nitroalkanes or
other compounds are classified as the Mannich reactions.
VII.2.d. Reactions with organometallic compounds
The addition of pentafluoroethyllithium to cyclic imines 79 Ph Scheme 102
Ph
affords pentafluoroethyl-substituted pyrrolidines and piper-
idines 102. The oxidative cleavage of 2-pentafluoroethyl- O
N O HCl, MeOH
2-furylpyrrolidine proved to be an effective route to a-pen- O
D
tafluoroethylproline (103) (Scheme 99).381, 382
Scheme 99 OMe
79i
Ph
1) C2F5Li, BF3 . Et2O, THF Ph
n
2) K2CO3, H2O O
R N O ...
N H
79 MeO
108 (83%, dr = 4 : 1) O
n
C2F5 O3, MeOH C2F5
R (R = 2-Fu, n = 1) CO2H
N N OH
H H N
102 (43% ± 65%) 103 (84%)
...
OAc N
N
OAc H
N Br OH Lycopodine
O
PhH, D
OMe O
79j OAc
109 (70%)
...
N
One more similar route to clavolonine has been
reported.387 Imine 79k used as the precursor was treated
with a methanol solution of HCl, which induced decarbox- OH Paniculine
ylation accompanied by epimerization of one stereocentre,
the subsequent Mannich reaction, acid-induced cleavage of R1 = H, OTIPS; R2 = H, Me; TBS = ButMe2Si, TIPS = Pri3 Si
methyl ether, the formation of enol ether and cyclization
(Scheme 104). Scheme 106
Scheme 104 H
R4COOH, R1
R1 +
R5NC R5 N C7
N N+
OBn R2 R4COO7 R2
ButO2C R3 R3
OBn +
N
N
a H R2
O R3
R1
H R R O
1 2
N
TBDPSO O R5 N N
H
R5 N R4
79k O R4
O R3
O
OBn
N OH
H N
The three-component Ugi reaction with 2-substituted
...
cyclic imines 79 opened up an effective route to proline and
O pipecolic acid derivatives with an additional substituent in
O
(96%) Clavolonine the a-position.391, 392 By means of the Ugi reaction, semi-
synthetic dipeptides 111 containing a natural amino acid
(a) HCl, MeOH, D; TBDPS = ButPh2Si moiety and a-substituted proline or pipecolic acid have been
prepared (Scheme 107).
Scheme 107
The Mannich reaction was also used in the synthesis of O
natural alkaloids: lycopodine 388, 389 and paniculine 390 n CH2Cl2 n
(Scheme 105). Instead of ketone, ketone silyl ether was + R2NC + R3CO2H
R1 NHR2
used. Bicyclic imines 79l were treated with zinc triflate to N N R1
afford tricyclic amines 110 in moderate or high yields. 79
C(O)R3
(115)
CbzCl, TMSOTf, CH2Cl2, 120 (66%) 121 (45%)
N
79m 778 ? 0 8C
AcO P(O)(OEt)2
+
CO2Me
O N
... O7
N
N DEPMPO
Oxaziridines possess a broad synthetic potential. They tend nucleophiles. In the case of 2-methylpyrroline (79h), depro-
to react with nucleophiles, undergo radical reactions and tonation occurs at the methyl group, and, after acylation,
some other types of chemical transformations. exocyclic aminoenone 128 is formed.405 It is of interest that
Scheme 114 trifluoroacetylation of imine 79p also involved the methyl
R2 mCPBA (MMPP) group of thiophene, resulting in the formation of compound
R1 129 in 39% yield (Scheme 116).
R3 N Scheme 116
79
R1 R1 O
R2 R2 n
+ F3C
R3 N R3 N + R N
O O n
cis-122 trans-123
R F3C O
N
[55% ± 98%, 122 : 123 = (2.1 ± 4.0) : 1] H
n LDA 127
R CF3CO2Et
126 (27% ± 67%)
R1 =Ph, Me; R2 = Alk; R3 = CO2Et N
79
The oxidation of imine 79o to desired oxaziridine 124 in
N
a good yield (76%) was reported.404 Product 124 was (R = Me,
H
n = 1) F3C
converted to new efficient reagent 125 for enantioselective O
oxidation of sulfides to sulfoxides (Scheme 115). 128 (78%)
79: R = Alk, Ar, Het; n = 1 ± 3
Scheme 115
O
1) LDA F3C
C8H17 C8H17
S 2) CF3CO2Et S
N N
H
mCPBA 79p 129 (39%)
...
O
Scheme 118
O
Ar O
O H
(133) O
O
O O
N Ar
O
O O H (79% ± 82%)
N C(O)Ar
H Me Me
O O O N O
N NH O N
(132)
131 N
N C(O)Ar O
O
C(O)Ar
O OH HO
O 134 (96% ± 97%)
922 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
5-arylfuran-2,3-diones 133 occurs on heating. In both cases, by NMR spectroscopy. However, on attempted isolation by
imine 131 reacts as the enamine tautomer. In the case of passing through silica gel, lactam 138 decomposed to be
compound 132, the addition of imine is followed by hetero- converted to amide 139. The other product formed in the
cyclization yielding polycyclic spiro-coupled product 134 reaction was tricyclic compound 140, which was isolated as
(Scheme 118). a by-product in 25% yield (see Scheme 120).409
Yet another type of cycloaddition reaction based on
VII.2.l. Cycloaddition reaction imines is the reaction of cyclic aza-allyllithium derivatives
Allenyl trimethylsilyl thioketenes undergo [4+2]-cycloaddi- generated in situ from stannanes 79q with alkenes 141 and
tion to imines 79 to give d-thiolactams 135.408 The starting polyenes 142a,b (Scheme 121). In most cases, [3+2]-cyclo-
thioketenes are generated in situ from propargyl sulfides 136 addition products 143 ± 146 were isolated in acceptable
upon [3,3]-sigmatropic rearrangement (Scheme 119). yields and with 1 : 1 ratio of regioisomers in the case of
alkenes 141 and 2 : 3 ratio in the case of cyclohexadiene
Scheme 119 (142a). Cycloheptatriene (142b) reacts with aza-allyllithium
to give cycloaddition product 147 and new cyclic imine 79r
TMS S
S with 1 : 1 product ratio and a total yield of 67% (see
R2 N TMS
TMS C N Scheme 121).410
S (79)
The same publication describes the reaction of azame-
R1 C R1 thine ylide generated in situ from pyrroline derivative 79q
R2
R1 with N-methylmaleimide (148). The [3+2]-cycloaddition
136 135 (56% ± 82%) products 149 were formed in moderate yields on refluxing
in toluene (Scheme 122).
R1 = H, Me, Ph; R2 = Me, Bun Scheme 122
Scheme 121
Bun R1 R1
R2
R3 R2 R3
(142a) (141)
HN + HN R1 SnBun3 NH + NH
BunLi, THF, 778 8C
N BunLi, THF, 778 8C
79q R3 R2
(R1 = Bun)
Bun 146 145 143 144
(68%, 2 : 3)
BunLi, THF, 778 8C
(R1 = Bun)
(142b)
Bun
NH
+
N
Bun 79r
R1 = H, Me, Bun, Ph;
143, 144: R2 = Ph, SPh, SePh; R3 = Ph, H 147 (67%, 1 : 1)
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 923
bifunctional reagents can be used in the synthesis of hetero- the same photocatalysts, development of selective reduction
cycles having an aminoalkyl moiety, some of the latter methods is in progress, for example, carbon dioxide reduc-
compounds, for example, tryptamines, exhibit clear-cut tion in cyclohexanol.440 In addition, the influence of various
physiological activities.411 ± 416 factors on the selective oxidation is investigated, for exam-
ple, the influence of water impurity,418 modification of
VIII. Photocatalysis in modern organic synthesis: semiconductors by doping with metals 441, 442 and non-
design of hybrid semiconductor metals 442 and so on.
Photocatalysis of the selective organic synthesis is per-
nanophotocatalysts formed using inorganic semiconductors with a particular
The synthetic methods considered in Sections II ± VII were band gap. As a rule, these are semiconductors based on
mainly implemented under conditions commonly used in nanostructured oxides and sulfides or their combinations.
organic chemistry (thermal activation, microwave treatment The selectivity of photocatalyst operation is determined by
and other). While analyzing the modern trends in the the band gap width and the defectiveness of the crystal
development of selective organic synthesis, one cannot but structure. The size of the band gap dictates the wavelength
pay attention to rapid growth of the interest in photo- range in which electromagnetic radiation is absorbed and
chemical, especially photocatalytic reactions.417 The advent the photocatalyst is activated. For example, for operation
of available and convenient equipment for practical imple- on exposure to visible light, the band gap (Eg) of the
mentation of photocatalytic reactions (light-emitting diode photocatalyst should be not more than 2.5 ± 3 eV. The
matrices, microreactor technology, reactors for effective use operation intensity, i.e., the catalytic activity, is caused by
of sunlight) has become an additional stimulating factor. a large free surface area of the photocatalyst, which is
In recent years, works dealing with selective transforma- achieved most efficiently by nanostructuring. As a rule, the
tions of organic compounds on inorganic photocatalysts smaller the particle size and the larger the surface area, the
have been published.418 ± 420 Although the number of these higher the catalytic activity per unit weight and unit volume
publications is still modest, selective transformations of of the catalyst. The intensity of photocatalyst operation also
organic compounds in the presence of photocatalysts acti- considerably depends on the concentration of active sites
vated by visible sunlight at ambient temperature are of and on the lifetime of the electronically excited state. Note
prime significance for preservation of the human health, that for increasing the photocatalyst activity and the quan-
increase in the quality of life and for environmental protec- tum yield of the reaction, it is necessary to take measures for
tion.421 ± 424 Indeed, the oxidation of organic pollutants of suppressing radiative transitions in the electronic subsystem
water and air photocatalyzed by inorganic semiconductors of the photocatalyst. It follows from the above that syn-
proceeds on exposure to sunlight and air oxygen, 425, 426 i.e., thesis of semiconductor photocatalysts with a specified
no oxidant needs to be added and no temperature change is band gap, small nanoparticle and nanopore size, high
required. The final products of this oxidation are harmless concentration of the active sites, long lifetime of the
water and carbon dioxide. Conduction of the selective electronically excited state and minimized probability of
synthesis under direct action of sunlight or visible artificial radiative transitions is a topical challenge of inorganic and
light provides direct conversion of the electromagnetic wave physical chemistry and solid-state chemistry.
energy to the chemical energy of the synthesized com-
pounds. Owing to the direct energy conversion on the VIII.1. Selective oxidation of organic compounds by
inorganic photocatalyst, i.e., the absence of intermediate photocatalysts activated by visible sunlight
stages of conversion, the energy expenditures for the The previously developed methods for the synthesis of
organic synthesis substantially diminish. Furthermore, the heavy metal chalcogenide nanoparticles (quantum
use of sunlight for selective oxidation is consistent with the dots) 443 ± 446 imply the use of a toxic organic dispersion
green chemistry concept, because it saves the energy-inten- medium, which considerably complicates the application of
sive natural raw materials and rules out the discharge of these procedures in environmentally friendly processes. One
hazardous wastes to the atmosphere.427, 428 of the ways for elimination of this drawback is to prepare an
The scope of applicability of selective oxidation of aqueous colloidal solution of cadmium sulfide nanoparti-
organic compounds includes cleaning of water areas, indus- cles.447 Aqueous solutions of cadmium chloride and sodium
trial wastes or air including indoor air, from hazardous sulfate are used as cadmium and sulfur ion sources, respec-
organic pollutants.421 ± 423 In addition, visible light-acti- tively, and a non-toxic aqueous solution of the disodium
vated photocatalysts can be used to perform water photol- salt of ethylenediaminetetraacetic acid (EDTA) is used as a
ysis.424 Selective organic synthesis making use of inorganic stabilizing agent to prevent coagulation of colloidal par-
photocatalysts is important not only for solving environ- ticles. At room temperature, this solution remains stable for
mental and energy problems, in particular, for the develop- a year, while at reduced temperature (4 8C), it is stable for 5
ment of so-called hydrogen power engineering, but also for years. The dispersion medium is non-toxic true aqueous
targeted synthesis of new functional materials, in particular, solution of sodium chloride and EDTA disodium salt.
for pharmaceutical industry.428 The obtained catalysts were studied by a set of phys-
Despite the fact that the first works on the selective icochemical methods.448, 449 A study of the size distribution
oxidation on metal oxide semiconductors were published of scattering sites found by the dynamic light scattering
more than 30 years ago,428, 429 only in the last decade, did technique demonstrated that most of the particles have the
substantial progress in this area take place.418 ± 420, 430 ± 439 size of 15 nm. This size includes the 1 nm thick layer of the
Currently, methods for selective oxidation of various stabilizing agent (small-angle neutron scattering data) and
organic compounds, e.g., cyclohexane,418 ethanol,419, 420 the 5 nm thick solvation shell. Thus, CdS nanoparticles in
glycerol 435 and so on are being actively developed. In aqueous solutions occur in micelles, which also contain
parallel with the oxidation processes actually catalyzed by stabilizing agent molecules and polarized solvent mole-
924 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
e7
CdS
3
Eg = 2.4 eV
H+/H2
TiO2
hn Eg = 3.2 eV
2 h+
1
CdS absorbs solar Heterojunction
20 30 40 50 2 y /deg light
Figure 11. X-Ray diffraction patterns of the TiO2@CdS composite Figure 12. Diagram of excitation of the active sites in the hybrid
xerosol (1), disperse phase of the aqueous colloidal solution of CdS semiconductor TiO2@CdS nanoparticle.
(2) and xerosol of the matrix TiO2 (3) recorded using CuKa1,2 The vertical line in the centre shows the nanoheterojunction
radiation.458 between the CdS nanoparticle and TiO2 . The electron transfer
The nanoparticles of the CdS disperse phase have a disordered from the CdS valence band is done by light quanta hn with >2.4 eV
closely packed structure (space group P6) and have a *3 nm size. energy.
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 927
The key problems that have not yet been solved in the
selective synthesis of organic compounds on inorganic semi- IX. Approaches of the surface science to the
conductor photocatalysts on exposure to visible light can be development of new catalytic systems for organic
divided into two groups. The first group refers to selection
of the optimal chemical and phase composition of the
synthesis
photocatalyst, while the second group concerns the tailored Currently, most of selective organic reactions are based on
synthesis (design) of particular photocatalysts. homogeneous catalytic systems, which have demonstrated
While selecting the optimal composition, it is necessary outstanding synthetic potential in a considerable number of
to solve problems related to adjustment of the photocatalyst important reactions (see Sections II ± VIII). Nevertheless,
band gap, combining the catalytic activity and photolumi- for scaling up the processes and decreasing the production
nescence, degradation of the photocatalyst with time, devel- cost, heterogeneous catalytic systems are still of prime
opment of methods for purification and regeneration of the importance. A number of heterogeneous catalytic processes
photocatalyst. The problem of adjusting the band gap can with selectivity compared with or even surpassing that of
be solved by nanostructuring, namely, by changing the size homogeneous processes can be regarded as very interesting
of nanoparticles or nanopores that form the active surface findings. However, for active introduction of heterogeneous
of the photocatalyst. In this regard, an important role is catalytic systems into the everyday practice of fine organic
played by the quantum confinement of excitons in the synthesis, it is necessary to bear in mind a number of
photocatalyst and by the optimal combination of phases of important specific features of the design of catalytic systems
hybrid photocatalysts. The suppression of photolumines- described below. Subsequent Sections X ± XII consider
cence for increasing the catalytic activity can be achieved by particular examples of implementation of in-demand syn-
reducing the probability of radiative transitions as a result thetic methods.
of affecting the electron and photon subsystems of the In recent years, a fundamental approach to the devel-
photocatalysts. The problem of activity decrease and regen- opment of new catalytic systems, including those for
eration of the photocatalysts should be solved considering organic synthesis, has become popular in the science of
the construction of the correct spatial distribution model for catalysis. A distinctive feature of this approach, as
active sites performing the oxidative and reductive reac- opposed to the more traditional empirical approach, is
tions. Furthermore, it is necessary to find methods for that the molecular design (controlled assembly) of the
catalyst treatment to remove the reaction products and active component is preceded by detailed investigations
other derivatives that are often deposited on the surface. of the mechanisms of catalytic reactions and structures of
In some cases, these deposits are very strongly attached to active sites. In the case of homogeneous catalytic proc-
the photocatalyst. esses where the catalytic reaction is a sequence of stoi-
The implementation of the tailored syntheses or, in chiometric steps of transformation of usual, although
essence, the design of the photocatalyst is related to selec- often intricate, chemical compounds, this approach can
tion and combination of synthetic procedures and to the be efficiently implemented by means of physical methods
search for new, in principle, synthetic methods. The tradi- sensitive to the molecular structure (e.g., NMR, EPR or
tional high-temperature methods (gas phase synthesis, IR spectroscopy). These methods are used not only to
chemical and physical vapour deposition, plasmochemical measure the concentrations of reactants and reaction
synthesis, self-propagating high-temperature synthesis) and products but also to determine the structures of inter-
low-temperature methods (chemical deposition, sol ± gel mediates. Thus, a detailed mechanism of the catalytic
procedures, solvothermal and sonochemical synthesis) are reaction can be determined.
used for this purpose. Development of new methods of The situation becomes much more complicated if we are
synthesis is based on the latest achievements of the physics, dealing with a heterogeneous catalytic process of organic
chemistry and biology. synthesis that is catalyzed by particles of noble metals (Pd,
When the photocatalyst has been manufactured, the Ag, Au, Pt) deposited on oxide or carbon supports with
question inevitably arises of what is the real mechanism of large specific areas (from ten to several hundreds of
the photocatalytic reaction. Here it is necessary to use both m2 g71). In this case, the low concentration of the active
ex situ and in situ methods, the latter becoming more and component (for noble metals, it usually does not exceed
more available. 1 mass % ± 2 mass %) is at the limit or even below the limit
The prospects for development of in situ methods with of sensitivity of many physical methods. This circumstance,
excitation of the electron and phonon subsystems of the together with the nonuniform size distribution of metal
photocatalyst directly during the photocatalytic reaction particles, complicates the measurements and isolation of
are very high owing to the advent of powerful sources of spectral characteristics of surface active sites responsible for
X-ray (synchrotron) and neutron radiations both all over the catalytic reaction.
the world and in Russia. Intense X-ray and neutron beams Solution to this problem became possible owing to the
can penetrate directly into the chemical reactor where the vigorous development of a field of knowledge adjacent to
photocatalytic reaction occurs and provide the experimen- heterogeneous catalysis, namely, the surface science, which
talist with information about the photocatalyst behaviour. is based on the use of surface-sensitive physical methods to
Owing to the development of targeted methods for the study the structure and composition of a solid surface.
synthetic design of complex nanostructures, it would Unlike standard methods, physical methods for surface
become possible to overcome the key difficulties of the investigation collect information only on several surface
selective synthesis. By using these nanostructures and sub- layers (up to 10 nm), which also makes it possible to study
stantiated combination of inorganic semiconductor phases, the surface structures of the adsorbed particles formed upon
it is possible to increase the yield of the product of organic reactant activation.
photocatalytic synthesis and increase the process selectivity.
928 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
The second foundation stone of the surface science 0.1 mass %± 10 mass %. Quite a few known patents propose
approach is investigation of the model catalysts in which introducing gold into the palladium catalyst to increase its
the surface concentration of the active component can be productivity.465
increased. Analysis of publications demonstrates that the
applied model catalysts can be subdivided into three large IX.1. Catalyst design and experiment setting up procedure
groups: Before proceeding to the results of investigations of the
(i) atomically smooth (low-index) and stepped single mechanisms of above-indicated catalytic reactions, it is
crystal surfaces (their definite surface structure is suitable necessary to discuss characteristic features of sample prep-
for studying structural effects); aration for model investigations.
(ii) supported monometallic particles on flat massive or
film supports (a change in the amount of sputtered metal IX.1.a. Single crystals
results in variation of the resulting particle size and, as a The interest of researchers in single crystals as model metal
consequence, in the possibility to study size effects); catalysts, which predominated in the 1970 ± 1990s, was due
(iii) supported bimetallic particles on flat supports (a to the quest for elucidating the effect of the surface structure
change in the coverage of the surface of metallic particles by on the nature of species formed upon adsorption of small
a particular metal achieved by varying the annealing tem- molecules and transformation steps of these species into the
perature and the ratio of metals taken provides the possi- intermediates and products of the catalytic reaction. The
bility to study the synergistic effects). preparation of single crystals with a definite surface struc-
Among modern trends of application of surface science ture for experiments starts with growing perfect single
approaches to catalysis, mention should be made of the crystalline rods of diameter *1 cm, which are then cut
development of physical methods of surface investigation along one of the crystallographic directions to form a
for in situ experiments, i.e., reactions in the presence of the 1 ± 2 mm-thick parallel-plate pellet, which thus restricts the
gas phase above the sample. Indeed, the pressure during contribution of the side surfaces with uncertain structure
catalytic measurements (P 5 1 bar) can be several orders of (<10%). The disorder of the principal faces of the pellet
magnitude higher than that used in surface science experi- should not exceed 1 deg (better, fraction of a degree) from
ments (P 4 1076 mbar) and, as a consequence, the chemical the chosen orientation. Cutting at a large angle provides
potential of the gas phase, which is ignored under ultrahigh- allows for the formation of stepped single crystal surfaces
vacuum (UHV) conditions, starts to make a significant with a strictly definite terrace size and monoatomic step
contribution to the free surface energy. This means that structure. The subsequent treatment of the single crystal
structures identified under unrealistic UHV conditions surface is performed in high vacuum chambers of spectrom-
could hardly play any role in catalytic reactions. The eters and, as a rule, involves the standard cleaning cycle
changes in the structure and composition of the surface repeated many times, comprising surface etching by argon
and near-surface catalyst layers taking place in this case can ions, heating in an oxygen atmosphere under specified
be of paramount importance not only for catalyst activity temperature conditions and the final UHV annealing at
but also for the whole reaction mechanism. premelting temperatures.
This Section is an attempt to demonstrate the potential
of surface science approaches as applied to investigation of IX.1.b. Supported metal particles on planar substrates
two comparatively simple catalytic organic reactions Ð The most popular method for the reproducible preparation
oxidative conversions of ethylene to ethylene oxide and to of model supported catalysts is the ultrahigh-vacuum dep-
vinyl acetate. The ethylene oxide synthesis by direct oxida- osition of disperse metal particles on a planar sup-
tion of ethylene with oxygen port.466 ± 468 When this preparation of metal nanoparticles
is carried out inside spectral equipment, it is possible, first,
C2H4 + 0.5 O2 C2H4O to pretreat and prepare of the support and the sputtering
system and, second, to transfer the prepared sample into the
discovered by Lefort 461 in 1935 is currently the best known analysis zone without contact with air. Thus, one can avoid
large-scale industrial process of organic synthesis using surface contamination and quickly prepare a series of
modified Ag/a-Al2O3 catalysts. The world consumption of samples with variable size of metal clusters. This circum-
ethylene oxide amounts to millions tonnes per year and stance accounts for the large number of studies that used
continues to increase.462 this technique to model real catalysts in order to study the
The synthesis of vinyl acetate from ethylene and acetic electronic properties and morphology of metal nanopar-
acid in the presence of oxygen ticles depending on their size. Attempts were also made to
study adsorption on disperse metal particles.469, 470
C2H4 + 0.5 O2 +CH3CO2H CH3CO2CH =CH 2 Despite the obvious advantages, for effective use of this
preparation technique in the catalytic studies, special pre-
can be accomplished as either a liquid-phase or vapour- cautions in the support preparation should be taken. On the
phase process. In the former case, the process is carried out one hand, the support should provide heating of the sample
in acetic acid with AcONa or LiCl additives in the presence up to the reaction temperature (as a rule, several hundred
of a homogeneous PdCl2 catalyst and CuCl2 at 110 ± 130 8C degrees) in the presence of the reaction medium, while the
and 1 ± 3 MPa.463 The vapour-phase synthesis of vinyl chemical composition of the support should remain invar-
acetate is conducted by passing a mixture of ethylene, iable, and ensure the stability of metal particles against
oxygen and acetic acid vapour through a solid catalyst bed sintering, on the other hand, the substrate should have a
at 100 ± 250 8C and 0.5 ± 1.0 MPa.464 Platinum metals, most good conductivity, which is required for investigations by
often, palladium supported on various porous materials scanning tunnelling microscopy (STM, measures the tunnel
serve as catalysts. The content of platinum metals is current between the tip and the conducting sample), X-ray
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 929
photoelectron spectroscopy (XPS, removing the electron 0.0715 mbar, and only a pressure increase to 1 mbar results
photoemission-induced charge leading to spectral line in the appearance of this signal starting from the temper-
broadening) and so on. These problems can be solved ature of 420 K.
without deterioration of the atomic smoothness of the The O1s core level spectra recorded under similar con-
support (which is necessary for STM determination of the ditions indicate that only nucleophilic oxygen (Onucl) char-
size of nanoscale metal particles) by using thin oxide films acterized by the O1s binding energy of 528.2 eV occurs on
[e.g., Al2O3 films grown on the surface of NiAl(110) the surface at low pressure. This state was observed in most
metallic single crystals 466] and highly oriented pyrolytic studies that used post-reaction analysis; it was shown that
graphite (HOPG) the surface of which is modified either this oxygen is active only towards the total oxidation of
chemically or by formation of induced defects.468 ethylene to CO2 and H2O. The pressure increase to 1 mbar
The procedural details of using physical methods for in results in a second component with a higher binding energy
situ investigations of the surface and adsorbed species appearing in the spectrum. Results of numerous experi-
during the catalytic reactions also deserve special discus- ments of this sort at different reactant ratios, temperatures
sion, which is beyond the scope of this Section (see, for and pressures made it possible to plot linear correlations
example, Ref. 471). between the concentration of this oxygen species and the
ethylene oxide yield (Fig. 14). This substantiated the
IX.2. Catalytic epoxidation and acetoxylation involvement of this oxygen, which was called electrophilic
IX.2.a. Ethylene epoxidation (Oel), in the ethylene epoxidation step.478
Despite the immense interest in the study of silver-catalyzed
ethylene epoxidation using physical techniques of surface
science,472 ± 477 the nature of oxygen species active in ethyl- 0.0016
400
1.05 mbar Onucl
1 CO2 + H2O
0.0715 mbar
RI is the reaction intermediate
0
100 200 300 400 500
Time /min More recently, it was shown that the formation of
electrophilic oxygen is related to considerable restructuring
of the initial silver surface, which is also caused by inter-
Figure 13. Change in the PTR-MS signals of ethylene oxide in
actions with components of the reaction medium at high
the reaction mixture vs. the sample temperature:
P(C2H4) = 0.0065 mbar, P(O2) = 0.065 mbar (1); P(C2H4) = 0.1 mbar, pressure.479
P(O2) = 0.95 mbar (2).478
The last part of the high-pressure curve is measured in the absence IX.2.b. Size effect in ethylene epoxidation
of O2. Yet another issue that would have not been resolved with-
out the use of model silver catalysts is interpretation of the
930 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
size effect in the epoxidation, which is manifested as an form agglomerates located near steps, that is, borders of
increase in the reaction rate by more than an order of atomically smooth surface terraces. In the case of the
magnitude upon the increase in the silver particle size to Ag/HOPG(Ar) sample with the initially defective surface,
>50 nm.480 Indeed, the intense O1s signal from alumina in the situation is quite different: silver nanoparticles are
`real' Ag/a-Al2O3 catalysts overlaps the signal from the uniformly distributed over the surface and have a rather
surface oxygen species, which made the XPS method non- narrow size distribution. Analogous conclusions can be
informative for identification of ethylene epoxidating oxy- drawn from the high-resolution SEM data (see Fig. 15 c,d ).
gen (Oel , see the previous Section). It was proposed to These results served for the development of a preparation
replace alumina by a carbon substrate, namely by HOPG. procedure for model Ag/HOPG catalysts having high
Owing to the atomically smooth surface of HOPG, this stability of Ag particles against sintering at elevated temper-
would enable using STM and SEM methods to determine ature, comprising the following stages: (i) etching of the
the silver particle size. This brings about two problems that HOPG surface with argon ions in order to create stabiliza-
are to be solved for successful in situ studies. The first tion sites for the silver particles being sputtered; (ii) silver
problem is related to the weak interaction of silver particles sputtering (it was shown that the amount of introduced
with the defect-free surface of the annealed pyrolytic graph- metal determines the average particle size); 3) heating of the
ite and, as a consequence, high mobility of silver particles pretreated surface at T 5 250 8C in a vacuum in order to
on the atomically smooth HOPG surface with the diffusion anneal defects and stabilize the surface of the model
coefficient reaching 1078 cm2 s71 (Ref. 481), which may catalyst.
result in fast agglomeration of the silver particles. The The stability of pyrolytic graphite against the oxidative
second problem is possible degradation of HOPG due to atmosphere was also verified by SEM. Figure 16 presents
burning of the carbon support under the oxidative atmos- the SEM images of the Ag/HOPG(Ar) sample after being
phere of the reaction. used in ethylene epoxidation experiments (O2 : C2H4 = 5 : 1,
For the solution of the first problem, a procedure for P = 0.25 mbar) at various temperatures for several hours. It
forming a defective HOPG surface by soft ion etching was can be seen that below 230 8C, the sample surface is stable
proposed. It was assumed that these defects would serve as (see Fig. 16 a), whereas the temperature rise to 250 8C
sites for crystallization and stabilization of silver particle.468 results in burning-out of graphite layers under diffusing
Figure 15 shows the STM and SEM images of two model and agglomerating silver particles (see Fig. 16 b). The
Ag/HOPG samples with equal atomic ratio Ag : C & 0.5 detected temperature limit of stability of pyrolytic graphite
prepared by UHV thermal sputtering of silver onto atomi- in the reaction medium in the presence of silver particles
cally smooth (sm) (see Fig. 15 a) and defective (see restricts the application of model Ag/HOPG catalysts for in
Fig. 15 b) graphite surfaces followed by annealing of sam- situ investigation of ethylene epoxidation to a temperature
ples at 250 8C. It can be seen that silver particles deposited of 230 8C, which, however, is high enough for ethylene
on a smooth HOPG surface sinter at high temperatures to oxide to be detected among the reaction products.478
a b a b
dz = 11.9 nm dz = 6.5 nm
Figure 16. SEM images (2506250 nm) of the Ag/HOPG(Ar) sur-
c d
face recorded after the sample has been used for many hours in
ethylene epoxidation experiments (P = 0.25 mbar) at 230 (a) and
250 8C (b).468
a b
530.8
531.9 533.9
532.8 531.9
530.8 529.2 532.8
533.9
210 8C 210 8C
190 8C 190 8C
170 8C 170 8C
150 8C 150 8C
526 528 530 532 534 536 538 526 528 530 532 534 536 538
Binding energy /eV Binding energy /eV
c d
10
Intensity (arb.u.)
0
0 50 100 150 200 250 0 50 100 150 200 250
Time /min Time /min
Figure 17. Photoelectron O1s spectra (a, b) and change in the mass spectrometric signal for ethylene oxide (c, d ) vs. temperature and time
for the Ag/HOPG samples with an average silver particle size of 8 (a, c) and 40 nm (b, d ).482
Experimental conditions: C2H4 : O2 = 2 : 1, P = 0.5 mbar.
behaviour can be interpreted based on analysis of the XPS specific features of the process such as the need to promote
spectra. The key distinctive feature of the O1s spectrum of the silver catalyst used in industry by chlorine and caesium
the coarse-particle sample is the presence of a peak with the compounds and the higher selectivity of bimetallic Ag7Cu
binding energy of 529.2 eV due to nucleophilic oxygen on catalysts in this reaction but can also help to develop
supported silver particles.482 The peak with Eb(O1s) = approaches to the design of the optimal silver catalyst for
530.8 eV is a superposition of two oxygen species Ð oxygen propylene epoxidation.483
dissolved in the surface layers of silver particles and O el
providing the formation of ethylene oxide (see Fig. 17 a,b). IX.2.c. Oxidative acetoxylation of ethylene
Peaks at higher binding energies correspond to oxygen- The ethylene adsorption as a p-complex is also the key
containing functional groups on the support surface.482 factor ensuring the high selectivity of oxidative acetoxyla-
Thus, it is the appearance of nucleophilic oxygen that tion of ethylene. Along with this desired reaction, other side
triggers the activity of silver in the ethylene epoxidation, reactions can occur in the system and thus decrease the
which accounts for the size effect.480 selectivity towards vinyl acetate (Scheme 124).
The question of why the presence of nucleophilic oxy- Scheme 124
gen, which is active in the total oxidation of ethylene,
C2H4 + 3 O2 2 CO2 + 2 H2O
increases the activity in the epoxidation, can be answered
by taking into account the transfer of electron density from CH3CO2H + 2 O2 2 CO2 + 2 H2O
silver to oxygen and formation of Ag+ ions.479 These silver
ions serve as sites of ethylene adsorption as p-complexes
CH3CO2CH =CH + 2.5 O
2 2 2 CO2 + 3 H2O
without activation of the C7H bond. Only after that, is the The contribution of these reactions has been esti-
adsorbed ethylene able to react with electrophilic oxygen to mated.484 It was shown that at the temperature of vinyl
give ethylene oxide either via the formation of oxymetalla- acetate synthesis (413 K),485 the rate of palladium-catalyzed
cycle 477 or directly.480 The reaction mechanism proposed oxidation of acetic acid is relatively low, and acetic acid
relying on model investigations can not only account for addition does not affect the kinetics of ethylene oxidation.
932 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
Similar experiments dealing with the effect of vinyl acetate the samples prepared in this way showed that in the case of
on the CO2 formation rate demonstrated that introduction a monometallic palladium sample, adsorption at 90 K gives
of 3.5 kPa CH3CO2CH CH2 into the reaction mixture = rise to a broad desorption peak with Tmax = 250 K. Upon
comprising ethylene, acetic acid and oxygen resulted in an introduction and increase in the content of gold, this peak
increase in the total oxidation rate by only 5%.484 Thus, it narrows down and the desorption maximum shifts towards
was concluded that the major contribution to the decrease lower temperatures (down to 215 K) (Fig. 18 a). In view of
in the selectivity towards vinyl acetate is made by the total the fact that in the case of bimetallic samples, D2 formed
oxidation of ethylene, which, in turn, depends on the type of upon C2D4 decomposition disappears from the TPD spectra
ethylene adsorption. (see Fig. 18 b), the low-temperature peak in the TPD spec-
The ethylene adsorption and decomposition have been trum of C2D4 was assigned to ethylene desorption from the
studied in detail by temperature-programmed desorption p-complex. Considering the intense D2 desorption peaks
(TPD) on model Pd/SiO2 and Au7Pd/SiO2 catalysts.486 recorded after adsorption on the monometallic palladium
Uniform heating of the sample, without which TPD experi- sample or on the samples with low gold contents (see
ments are impossible, has been provided by a special design Fig. 18 b), the high-temperature shoulder in the TPD spec-
of the model catalyst based on a refractory molybdenum trum of ethylene was identified as desorption from the di-s-
single crystal. A SiO2 film grown epitaxially on the Mo(110) state, which is the intermediate for the total ethylene
surface is complementary to the metal structure.487 One oxidation pathway.486 These data demonstrate that the
monolayer (ML) of palladium and then gold in different introduction of gold changes the surface composition of
amounts (from 0.1 to 1 ML) were sputtered on the prepared particles.
SiO2 film and then the samples were annealed in a vacuum The surface composition of the prepared bimetallic
at 800 K. A study of adsorption of deuterated ethylene on catalysts was studied by the ion scattering spectroscopy
(ISS),488 while the atomic structure of the surface sites was
investigated by IR spectroscopy.489 These experiments were
a carried out using model samples of a different type in which
250 K gold and palladium were successively sputtered onto a
cleaned surface of the Mo(110) face. Owing to the high
melting point of molybdenum, the samples could be heated
230 K up to the gold (1400 K) and palladium (1420 K) desorption
MS signal at m/z 30
a a
2087 cm71
Mo Pd Au 0.0025
1300 K
2105 cm71
4000
Intensity of the ISS signals (arb.u.)
Absorbance (arb.u.)
1100 K
7
3000 1000 K
0.0015
900 K
6
800 K
2000 700 K 0.0010
5
600 K
500 K 4
400 K 0.0005
1000 Pd/Au/Mo(110) 3
2
0 1
Au/Mo(110)
0
2200 2100 2000 1900 1800 1700
0.90 0.95 1.0 1.05 1.10
Wavenumber /cm71
Kinetic energy /keV
Absorbance b
b 2087 cm71
1
100 0
2 0.1%
Concentration of Pd (at.%)
Concentration of Au (at.%)
80 20 2112 cm71
60 40 7
40 60
6
20 80
0 100 5
200 400 600 800 1000 T /K
4
Figure 19. Ion scattering spectra of the Pd(5 ML)/Au(5 ML)/
Mo(110) sample depending on the annealing temperature (the 3
spectra were recorded at room temperature after annealing at the 2
specified temperature for 20 min) (a); surface concentrations of Au
and Pd in the samples: Pd(5 ML)/Au(5 ML)/Mo(110) (1) and 1
Au(5 ML)/Pd(5 ML)/Mo(110) (2) depending on the annealing 2200 2100 2000 1900 1800
temperature (b).488 Wavenumber /cm71
adsorbed on palladium sites in the sample annealed at lower The aspects of synthesis of bimetallic nanoparticles are
temperature. This is indicated by the signal at *2030 cm71 considered in detail in a number of reviews. A review by
(Ref. 495), which appears in the spectrum in addition to the Chandler and Gilbertson 501 is devoted to the synthesis,
intense signal at 2050 ± 2080 cm71 due to the terminal investigation and application of dendrimer-encapsulated
species COads/Pd.494 Because of weak interaction of CO bimetallic particles. Liquid-phase synthesis and catalytic
with gold (8 ± 10 kcal mol71) (Ref. 497), the contribution of applications of bimetallic nanocrystallites have been ana-
COads/Au to the IR spectra recorded at room temperature lyzed in a considerable detail in a review.502 Techniques for
(see Fig. 20) should be excluded. This result indicates that in the preparation of bimetallic particles of a specified geom-
the equilibrium state, the surface of the Pd7Au alloy etry by up-to-date methods of colloidal chemistry are
contains only single palladium atoms surrounded by only comprehensively described in reviews.503 ± 505
gold atoms. As a consequence, ethylene can be adsorbed on A considerable contribution to understanding of the
this surface only as p-complexes. Annealing at lower tem- relationship between structural features of small metal
perature retains some neighbouring palladium atoms. The particles, including bimetallic particles, is made by
possible formation of di-s-complexes by adsorbed C2H4 advanced physicochemical investigations, especially per-
would increase the probability of the total oxidation path- formed in situ, i.e., directly during the catalytic reac-
way for ethylene, thus decreasing the process selectivity with tion.506, 507
respect to vinyl acetate. A practically important recommen- Unfortunately, very few reviews are devoted to the
dation that follows from the performed fundamental application of bimetallic catalysts and bimetallic nanopar-
research of the oxidative acetoxylation of ethylene on ticles in organic synthesis. These issues are covered most
model Pd7Au catalysts is to use high annealing temper- comprehensively in reviews by Cai et al. 508 and by Yu et al.
atures. (devoted to platinum-based catalysts).509 The use of hetero-
Taking into account these recommendations, the geneous bimetallic and nanocomposite catalysts in organic
Pd(1%)7Au(0.5%)/SiO2 catalyst was prepared by incipient synthesis is considered in a review by Shi.510 This Section
wetness method and annealed at 500 8C.498 Comparison of deals with synergistic effects observed in the reactions
its catalytic properties with those of the monometallic conducted on heterogeneous nanocomposite catalysts. It
Pd(1%)/SiO2 catalyst prepared in a similar way showed 499 was stated 511 that the causes of synergistic effects for
that the addition of gold increases by more than an order of various catalytic systems significantly differ and cannot
magnitude the catalyst activity expressed as the number of always be generalized, because they depend on the specific
vinyl acetate molecules formed in 1 s on one surface character of a particular catalytic system (catalyst + the
palladium atom; the selectivity in this case reaches 96% reaction it catalyzes). Within the framework of this Section,
(for comparison, the best monometallic catalyst provides we made an attempt to analyze the available published data
only 90% selectivity).498 High annealing temperatures on the use of bimetallic catalysts in some important reac-
(500 ± 600 8C) are also indicated in modern patents devoted tions of fine organic synthesis including selective hydro-
to improvement of palladium ± gold supported catalysts for genation and cross-coupling.
vinyl acetate synthesis.500
Thus, the understanding of the mechanisms of catalytic X.1. Hydrogenation of alkenes, alkynes, carbonyl
reactions and determination of the active site structure may compounds and nitro compounds
serve for pronounced improvement of the reaction selectiv- The selective hydrogenation of compounds containing
ity towards the target product. The use of this approach will = =
C C and C O bonds is a fairly topical task, because
be extended in the near future; however, there are some the unsaturated products thus formed are used to prepare
obvious limitations to applying it to complex organic fragrance alcohols and biologically active compounds and
reactions in the liquid phase. The first step in solving this are also widely employed in pharmaceutics. The key
problem may be the post-reaction analysis of heterogeneous obstacle interfering with the selective process is that hydro-
catalysts by surface-sensitive physical methods for detection =
genation of the C C bond is *35 kJ mol71 more thermo-
of changes in the structure and chemical state of the surface dynamically favourable 512 than hydrogenation of the
upon the catalytic reaction. The atmosphere-free loading =
C O bond. Nevertheless, analysis of the modern literature
technique (dry chamber) becomes especially significant for indicates that the use of bimetallic catalysts is an effective
transfer of samples from the reaction medium inside spec- method for increasing both the activity and selectivity of the
trometers or microscopes. Yet another direction for the reaction.
development of this area is to choose simple compounds The efficiency of the monometallic Pt/SiO2 catalyst and
that model some organic reaction (hydrogenation, oxida- supported bimetallic (Co7Pt/SiO2 , Cu7Pt/SiO2) catalysts
tion, functionalization, etc.). has been studied in detail in the hydrogenation of cinna-
Scheme 125
X. Bimetallic catalysts in organic synthesis
OH
Although bimetallic catalysts have been used for rather long
time, there has been a boom in the research in this area in Co7Pt R
recent years, which is reflected in the enormous number of O
publications. This trend is due to both the advances in the H2
O
R
elaboration of synthetic routes to nanostructured materials 75 8C
and the development of the physicochemical methods for Cu7Pt R
150a ± d
their research including the appearance of in situ proce-
dures.
R = H (a), Me (b), Ph (c), OEt (d)
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 935
maldehyde (150a).513 Platinum catalyst promotion by cubic nanocrystals, the activity decreases almost twofold.
cobalt or copper markedly increases its activity (the con- The introduction of Ni results in the turnover frequency
version over a period of 2 h increases from 4.8% to increasing from 23 to 139 h71 and in a substantial increase
10% ± 28%). Apart from the increase in the activity, the =
in the C C bond hydrogenation selectivity, the carbonyl
introduction of the second metal provides the possibility for group remaining almost intact.
controlling the process selectivity. Indeed, the catalyst Scheme 127
promotion by cobalt enables selective hydrogenation of (111) (111)
=
the C O bond, while the introduction of Cu results mainly O O
=
in C C bond hydrogenation (Scheme 125).
(111)
Similar results were obtained by Bertero et al.514 It was
found that modification of a Pt catalyst by cobalt makes it H2 (1 atm), rt
150b
possible to suppress undesirable hydrogenolysis and decar-
bonylation processes in the liquid-phase hydrogenation of
citral (151) and thus increase the catalyst activity and to It was shown 518 that the activity and selectivity of Pt
control the selectivity towards the formation of either catalysts in the cinnamaldehyde hydrogenation can be
geraniol (152) or citronellal (153) and citronellol (154) increased upon the catalyst modification with tin. The
(Scheme 126). selectivity of formation of cinnamic alcohol grows following
Scheme 126 an increase in the Sn : Pt ratio to 0.8. It is noteworthy that
the process rate also grows reaching a maximum at
Sn : Pt = (0.2 ± 0.4). The beneficial effect of Sn on the
* selectivity of cinnamaldehyde hydrogenation was confirmed
in another work.519 Also, the researchers demonstrated that
OH OH a similar effect can be induced by modifying the Pt catalyst
with gallium. It should be noted that the crucial factor is the
152 154 presence of clear-cut interaction between Pt and the mod-
O ifying component, which was achieved by means of the
reductive deposition ± precipitation technique developed by
* the authors.
151
In conclusion, mention should be made of the catalytic
O
=
systems able to perform C O bond hydrogenation using
such hydrogen sources as hydrazine or NaBH4 , which is of
153 much interest for laboratory practice. The use of bimetallic
Rh7Co particles was shown 520 to provide effective hydro-
In another work,515 a highly selective catalyst based on =
genation of the C C double bond in unsaturated ketones
Pt7Co nanoalloy particles was prepared by decoration of =
and esters, the C O bond remaining unaffected.
Pt nanocrystals with Co atoms under controlled conditions
using a colloidal solution. By using cobalt-decorated plati- X.1.a. Selective hydrogenation of alkynes
num nanoparticles, the researchers were able to perform The catalytic hydrogenation of alkynes has a fundamental
=
highly selective hydrogenation of the terminal C O group value both for laboratory practice and for chemical indus-
of cinnamaldehyde, while completely suppressing the unde- try,521 because it can create trans- and cis-alkene moieties
=
sirable hydrogenation of the C C bond as a result of serving as building blocks in fine organic synthesis. The
blocking of low-coordinate Pt sites and optimization of the hydrogenation is typically catalyzed by supported metallic
electronic properties of Pt nanoparticles by means of Co catalysts. Therefore, numerous research teams all over the
addition. world are engaged in the research of the main regularities of
The reason of an increase in the selectivity of hydro- the catalytic action of these materials.522, 523 The key goals
genation when catalyzed by bimetallic catalysts, including are, first, to minimize the conversion of alkenes formed in
Pt7Co, was studied theoretically by Murillo et al.516 using the reaction to alkanes and, second, to select process
surface science approaches and density functional theory conditions that would result in the desired stereoselectivity.
(DFT) calculations. It was found that the increase in the For cis-alkene synthesis from alkynes, the heterogene-
=
selectivity of C O bond hydrogenation in the acrolein ous Lindlar catalyst (Pd7Pb) is often used. A considerable
molecule conducted on the Pt7Co7Pt(111) surface is drawback of this catalyst is the toxicity of lead compounds,
related to the increase in the energy of the di-s-C7O which are needed for partial catalyst deactivation for
bond between the intermediate and the catalyst surface; preventing the reduction of the target products (alkenes)
the more electropositive metal (Co) acts as the electron- to alkanes. In addition, this catalyst is inapplicable to some
donating ligand and increases the electron density on the substrates. For example, terminal alkynes cannot be selec-
=
surface Pt atoms. As a result, the C O bond hydrogena- tively converted to alkenes as they are rapidly hydrogenated
=
tion accelerates, whereas the C C bond hydrogenation to alkanes. In some cases, the use of the Lindlar catalysts is
slows down. accompanied by instability and irreproducibility of the
Interesting results have been obtained by Wu et al.,517 results under experimental conditions.524
who showed that the activity of bimetallic catalysts in the A promising way for attaining selective hydrogenation
benzylideneacetone (150b) hydrogenation is determined by of the C:C bond is the use of bimetallic catalysts. The
not only the composition but also the shape of bimetallic studies along this line carried out to date demonstrated that
alloy nanoparticles (Scheme 127). The highest reaction rate the highest selectivity results from the use of bimetallic
is achieved with octahedral particles, while on going to catalysts containing a Group 8 metal (usually Pd) as one
936 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
of the active components.525, 526 The key role is then played resulting in partial oxidation and pronounced surface seg-
by two factors: the nature of the second metal and the regation of gallium.
degree of homogeneity of the bimetallic nanoparticles that Nevertheless, in some cases, the results of the gas-phase
are formed during the catalyst preparation. and liquid-phase hydrogenation are well correlated with
For example, the introduction of Zn or Ag into a Pd each other. Thus for catalysts based on the bimetallic
catalyst considerably increases the selectivity in alkyne complexes PdM(OAc)4(OH2) (M = Zn, Ce, Co, Ni), it was
hydrogenation to alkenes, although the activity somewhat found that introduction of the second metal leads to higher
decreases.527 The observed increase in the selectivity to selectivity of diphenylacetylene hydrogenation, as in the
alkenes is usually attributed to electronic and/or ligand case of gas-phase hydrogenation, and results in higher
effects and to the disappearance of the palladium hydride percentage of the target cis-isomer in the reaction products.
b-PdH phase. The two first-mentioned factors are tightly It was shown that the activity of catalysts deposited from
interrelated. The presence of the second metal on the bimetallic complexes considerably depends on the nature of
surface and in the bulk of a bimetallic alloy particle the second metal and increases in the order
changes the electronic properties, resulting in a decrease PdZn < PdCo < PdNi.535 Therefore, the results confirm
in the desorption energy of the alkene being formed, which good perspectives for the catalysts based on bimetallic
thus becomes lower than the activation energy of the palladium acetate complexes in the selective hydrogenation
second (alkene ? alkane) hydrogenation step. Hence, of C:C bonds.
alkene desorption rather than further hydrogenation Homogeneous bimetallic particles can also be prepared
becomes the predominant reaction pathway. 528 The sec- in solution. Spee et al.536 reported a detailed investigation of
ond, geometric effect of the introduction of the second the catalytic properties of the Pd7Cu/SiO2 bimetallic
metal is `dilution' of the Pd surface layer by inactive metal systems in the selective hydrogenation of substituted
atoms, which reduces the probability of formation of alkenes and propargyl alcohols. The Pd7Cu nanoparticles
multiatomic sites in which strong multicentre adsorption were obtained by the reaction of lithium di(4-tolyl)cuprate
of alkylidene intermediates is possible. These intermedi- with palladium acetate, resulting in deposition of Pd7Cu
ates are believed to be responsible for the direct hydro- particles on the silica gel surface. The formation of the
genation of alkynes to alkanes.529 Pd7Cu alloy was verified by high-resolution electron
A considerable role is also played by the degree of microscopy and EXAFS. The Pd7Cu/SiO2 catalysts dem-
homogeneity of the prepared bimetallic nanoparticles. In onstrated much higher selectivity than the Lindlar catalyst
the ideal case, the composition of every nanoparticle should towards the formation of cis-alkenes in the hydrogenation
correspond to the component ratio of the whole catalyst; of mono- and disubstituted alkynes.
however, obtaining this high degree of homogeneity is a Interesting results of selective hydrogenation of terminal
challenging task. An effective process for the preparation of alkynes were obtained in the already mentioned study by
highly homogeneous bimetallic catalysts is the use of Lin et al.520 It was found that bimetallic Rh7Co nano-
heterobimetallic palladium acetate complexes with the sec- particles provide high yields of terminal alkenes and diphe-
ond metal PdM(OAc)4(OH2) (M = Zn, Ce, Co, Ni).527, 530 nylethylene (Scheme 128). Hydrazine hydrate served as the
These catalysts are more active in the hydrogenation of hydrogenating agent and, hence, the reaction could be easily
alkynes to alkenes than the catalyst samples prepared by the conducted using common laboratory ware for organic syn-
traditional deposition of the metal precursors from solu- thesis.
tions of individual salts.527 Scheme 128
An ingenious method for increasing the selectivity of R2
bimetallic catalysts for hydrogenation of alkynes to alkenes [H], cat
is the use of intermetallic compounds in which the electronic
effect of the second component on the adsorption and R2
R1 R1
catalytic properties of the active metal is much more
pronounced than in disordered alloys. Indeed, it was ascer- R2 = H: R1 = H, Me, But, F, Br; R1 = H, R2 = Ph
tained 531 that the Ni3Ge/MCM-41 catalyst performs highly
selective hydrogenation of acetylene in an excess of ethylene [H], cat
up to almost complete conversion of the alkyne. Similar Bun Bun
results have been obtained 532, 533 for the intermetallic com-
pounds PdGa and Pd3Ga7 . A new method for the preparation of bimetallic Rh7Ag
It should be noted, however, that the results of reactions nanoparticles has been proposed,537 namely, entrapment of
of fine organic synthesis in the liquid phase catalyzed by the catalytically active Rh within a silver metal matrix. This
supported bimetallic catalysts are not always consistent was done using an original procedure based on reduction of
with the results obtained for the gas-phase heterogeneous AgNO3 with Zn metal to give finely dispersed Ag in
catalysis. For example, liquid-phase hydrogenation of phe- solution. This is accompanied by entrapment of the Rh
nylacetylene on the above-mentioned PdGa intermetal- complex, giving rise to a bimetallic particle. This Rh7Ag
lic 532, 533 showed only a minor increase in the selectivity complex showed high selectivity towards the formation of
with respect to that on monometallic Pd catalyst.534 Fur- cis-stilbene. This result is even more notable because mono-
thermore, it was found that the same is true for the Lindlar metallic Rh nanoparticles provide the formation of only
catalyst. The authors attributed these significant discrep- exhaustive hydrogenation products.
ancies of the results obtained for the gas-phase hydrogena- The synthesis of trans-alkenes from alkynes is a more
tion of acetylene and liquid-phase hydrogenation of complicated task than the synthesis of cis-alkenes by the
phenylacetylene to specific effect of the liquid phase on the hydrogenation reaction. An ingenious method for the syn-
surface chemistry of the PdGa intermetallic compound, thesis of trans-isomers upon diphenylacetylene hydrogena-
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 937
tion was proposed by Komatsu et al.538 Using the SnO2 has a much higher activity and selectivity in the
Pd3Bi/SiO2 catalyst containing a palladium intermetallic hydrogenation of 2-chloronitrobenzene compared with
compound as the active component, the authors were able Pt7Ru/SnO2 prepared by the classical impregnation
to achieve high selectivity in the transformation of diphe- method. Physicochemical measurements demonstrated that
nylacetylene to cis-stilbene up to a >90% conversion. The the higher activity of the catalyst based on nanoparticles is
catalyst shows much higher selectivity than the classical due to a smaller particle size and a narrower particle size
Lindlar catalyst. By using Pd3Bi/SiO2 as the hydrogenating distribution of the bimetallic alloy.
component and by mechanically mixing it with the H-USY The highly active bimetallic catalysts based on fine
zeolite, the authors achieved a *74% yield of trans- nanoalloy particles are able to perform the selective hydro-
stilbene. The Pd3Bi/SiO2 catalyst performs the selective genation of the nitro group under relatively mild conditions
hydrogenation of diphenylacetylene to cis-stilbene, whereas and, therefore, they are of considerable value for laboratory
on the zeolite component, the resulting cis-stilbene isomer- practice. It was shown, for example,544 that unsupported
izes to the thermodynamically more stable trans-product Rh3Ni nanoparticles catalyze the reduction of the NO2
(Scheme 129). group of 4-nitrobenzaldehyde with molecular H2 at room
Scheme 129 temperature (Scheme 130). Product 155 is formed with a
selectivity of > 99% at virtually complete conversion of the
H2, Pd3Bi
initial compound. It was found that the Rh3Ni catalyst
ensures effective reduction of the NO2 group in nitroaro-
matic compounds containing diverse functional groups and
can be reused many times without substantial activity loss.
H+
Scheme 130
NO2
H2, cat
rt
X.1.b. Reduction of the nitro group OHC
The reduction of the nitro group of substituted aromatic NH2 NH2
compounds is of considerable interest both for laboratory +
organic synthesis and for the industrial production of OHC HOH2C
various pharmaceuticals, polymers, dyes, etc. Unfortu- 155
nately, many currently existing catalysts do not meet the
high activity and selectivity requirements simultane- Yet another notable result that presents considerable
ously.539, 540 On the one hand, the classical systems such as interest for laboratory practice was reported by Jiang
Pd/C are highly active but they do not provide the sufficient et al.545 A catalyst containing Au7Ag nanoalloy as the
process selectivity because of undesirable by-products for- active component was prepared by depositing pre-synthe-
mation, and an additional step for the target product sized bimetallic Au7Ag nanoparticles onto a metal-organic
purification is required. On the other hand, catalysts that framework (MOF). This catalyst is suitable for nitrophenol
show high selectivity require conducting the reactions at reduction with NaBH4 in an aqueous solution. The authors
high temperature and high hydrogen pressure due to their showed that the crucial role is played by the structure of
low activity. Bimetallic catalysts help to overcome this Au7Ag nanoparticles. The best results were found for
problem and carry out the process under relatively mild particles with the core ± shell structure (Ag core and Au
conditions with the required selectivity. shell; AushellAgcore), while the monometallic Au catalyst and
In a detailed study of the bimetallic Pd7Au/Al2O3 a catalyst based on disordered Au7Ag alloy were substan-
catalysts,541 the catalysts were prepared by the deposi- tially less active.
tion ± precipitation technique and by the conventional
impregnation technique; the atomic Au : Pd ratio varied X.2. Cross-coupling reaction
from 8 to 88. It was found that the introduction of Pd in X.2.a. Suzuki cross coupling
the ratio Au : Pd = 20 results in a threefold increase in the A typical example of the Suzuki reaction is the coupling of
activity, while maintaining exceptionally high selectivity arylboronic acid and aryl halide to give substituted biphenyl
towards the formation of 4-chloroaniline from 4-chloroni- (Scheme 131). The most efficient catalyst for this reaction is
trobenzene. Pd (both as complex compounds and as the metal); there-
It was also found 542 that the bimetallic Pd7Au catalyst fore, Pd-based catalysts are vigorously studied (see Sec-
shows an exceptionally high activity in the selective hydro- tion VI.2). Catalysts containing bimetallic Pd7M particles
genation of 2-chloronitrobenzene to the corresponding can efficiently solve problems of increasing the catalyst
amine. The Pd7Au catalyst proved to be substantially activity, selectivity and stability and help to elucidate details
more active than the monometallic Pd sample. In this of reaction mechanisms.
study, the bimetallic nanocatalyst stabilized by polyvinyl- The bimetallic Pd7Au catalysts find rather wide use in
pyrrolidone (PVP) was prepared by dropwise addition of the Suzuki cross-coupling reaction owing to higher activity
solutions of the precursors (PdCl2 and HAuCl4) to a and stability of the catalytic action. For increasing the
colloidal solution of the support (activated carbon) and activity and stability of Pd catalysts, Tan et al.546 used
PVP. The high activity of the obtained sample made it bimetallic Au7Pd nanoparticles enclosed in SiO2 nano-
possible to carry out hydrogenation under relatively mild spheres. Both the Au : Pd ratio and the nanoparticle
conditions (50 8C, 3 atm of H2). structure were varied over broad limits. It was found
Liu et al.543 found that the bimetallic Pt7Ru catalyst that the catalytic activity increases in the series
prepared by deposition of the Pt7Ru nanoparticles onto Au < Pd < PdshellAucore < AuPd3 < AuPd < Au3Pd. It is
938 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
of interest that alloyed Au7Pd@SiO2 particles with the A somewhat different conclusion was drawn by Fang et
lowest Pd content had the highest catalytic activity and al.,553 who used nanoparticles with the PdshellAucore struc-
selectivity. The use of the SiO2 shell for Pd stabilization ture to elucidate the mechanism of the Suzuki reaction and
prevented the particles from agglomeration during the the effect of Pd leaching on the overall reaction mechanism.
process. In addition, the effect of Pd leaching from the Cyclic voltammetry and inductively coupled plasma mass
catalyst is markedly suppressed for these nanoparticles. It spectrometry measurements showed that Pd leaching may
was found that the Pd content in the reaction solution after be caused by joint action of the base and arylboronic acid
the AuPd@SiO2-catalyzed process is *51 ppb, whereas for rather than by oxidative addition of aryl halide.
commercial Pd/C catalyst, this value can be as high as The introduction of a non-noble 3d metal having ferro-
650 ppb. magnetic properties into the Pd7M nanoparticle (M = Ni,
Scheme 131 Co, Fe) facilitates the separation of the catalyst from the
reaction medium and increases the stability of catalyst
[Pd], K2CO3
X + (HO)2B operation. Wu et al.554 carried out the cross-coupling
solv7H2O
R1 R2 reaction using Pd7Ni nanoparticles of a definite size
R2 (*10 ± 15 nm) and shape. The introduction of Ni into Pd
nanoparticles resulted in a considerable increase in the
R1 catalytic activity as compared with the monometallic Pd
nanocatalyst: the yield of the target product reached *90%
R1 = 4-Me, 4-OMe, 4-NH2, 4-Ac, 2-NH2, H; R2 = H, F, 4-NH2; at 80 8C. Moreover, even at room temperature, the reaction
X = Br, I; solv is organic solvent. occurred with a yield of up to 40%. Note that the catalytic
Conditions: 0.0235 mmol of Pd, 0.25 mmol of Au, 1.1 mmol of activity of the Pd7Ni nanoalloy increases with increase in
boronic acid, 3 mmol of K2CO3, 1 mmol of aryl halide, the Ni content up to Pd50Ni50 , and, hence, the consumption
EtOH : H2O = 2 : 1 (25 ml), 70 8C, 24 h of the expensive noble metal can be decreased. The Pd7Ni
catalyst is fairly stable and can be used for up to 5 times
without loss of activity. Owing to the presence of Ni in the
R1 R2 Conversion (%) alloy structure, the nanoalloy particles can be magnetically
separated from the reaction products.
Pd Pd ± Au Magnetic separation of the catalyst from reaction prod-
ucts is also possible for Pd7Co nanoparticles. Alonso
4-Ph H 0 88 et al.555 prepared catalytic PdshellCocore particles supported
4-Me H 4 100 on a polymer and distributed in the polymer surface layer.
H 4-F 58 100 In the presence of this catalyst, the yield of the target
2-NH2 H 0 6 product in the Suzuki cross-coupling reached 95% ± 100%
H 2-NH2 98 36 after 18 h at 70 8C. The reaction was carried out in a
DMF7H2O mixture (4 : 1); upon the increase in the H2O
A comparison of the catalytic activities of Pd7Au and content from 10% to 20% ± 40%, the yield of the reaction
monometallic Pd catalysts has been reported. 547 It was product increased from 20% ± 40% to 80% ± 90%.
shown that on introduction of electron-donating groups An example of application of bimetallic catalysts for
into aryl halides, the bimetallic catalyst shows a much cross-coupling has been reported by Kim et al.556 The
higher activity; a similar effect is induced by introduction authors prepared mono- and bimetallic nanoparticles stabi-
of electron-withdrawing substituents (e.g., F atom) into lized by PVP and supported on the Vulcan XC-72TM carbon
arylboronic acid (see Scheme 131). support. The reduction to the metal was accomplished
It is noteworthy that in the series of aryl halides, the without chemical reducing agents on exposure to g-radia-
activity varies as I > Br 4 4 Cl and that bimetallic Pd7Au tion. The alloy formation was confirmed by powder X-ray
catalysts show much higher activity when `inert' sub- diffraction based on the characteristic shift of reflections
strates such as bromobenzene are used. Presumably, the corresponding to Pd(111). The catalytic activities of the
introduction of Au leads to acceleration of the rate-limit- obtained catalysts were studied in the Suzuki cross-coupling
ing oxidative addition step and, hence, Pd7Au catalysts performed for 3 h at 78 8C. The highest activity was found
provide much higher conversion for a broad range of for the Pd7Cu/C samples where the yield reached
substrates than the monometallic Pd catalyst. These 96% ± 97%. The catalyst activity varied in the sequence
results are in good agreement with the results of another Pd7Cu/C > Pd/C > Pd7Ag/C > Pd7Ni/C. The most
publication 548 in which the highest catalytic activity was valuable characteristics of the bimetallic catalyst is high
achieved for catalysts with the Pd shell Aucore structure. The stability: for five successive catalytic cycles, the product
key role of the oxidative addition giving rise to the yield was found to somewhat decrease in the first cycle and
ArPd II X species has been confirmed by Shi. 510 It was then the catalyst activity was found to remain almost
shown that the Pd/NiFe 2 O 4 composite catalyst has a invariable.
high catalytic activity owing to the electron density don-
ation from NiFe 2 O4 to Pd nanoparticles. Note that, X.2.b. Sonogashira cross-coupling
generally, this fact is in good agreement with experimental Yet another reaction widely used in organic synthesis for
data, indicating enhanced catalytic activity of the Pd the formation of the C7C bond is the Sonogashira reac-
catalysts supported on basic supports.549 ± 551 This conclu- tion, which is the cross-coupling of vinyl and aryl halides
sion was confirmed 552 for both the monometallic Pd/C with terminal alkynes to give arylacetylenes and conjugated
catalyst and bimetallic Pd7Au/C and Pd7Au/SBA-15 enynes.557 This reaction requires elevated temperatures and
samples (SBA-15 is a silica brand). occurs in the presence of Pd catalysts.
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 939
nature. More basic nitrogen-containing groups arising upon unexpected and exceptionally interesting information on the
carbon calcination at 900 8C in the presence of NH3 give use of the mesoporous graphite-like material Sibunit as the
rise to a higher catalyst efficiency than weakly basic oxygen- catalyst.575 As compared with the conventional coking coal,
containing groups, which are similar to g-pyrone groups which is highly structurally disordered, all other factors
and are formed as carbon pre-calcined under inert atmos- being the same, the use of Sibunit resulted in a much lower
phere comes in contact with air at room temperature. amount of CCl4 by-product (only 50 ppm) and a 10 times
Although the reaction mechanism is still unknown, it has longer service life. Even after two years of operation in an
been demonstrated to date that nitrogen-containing carbons industrial reactor (80 8C, 4.83 bar), the performance of this
are fairly efficient in O2 activation. catalyst remained at an acceptable level.
Yet another vivid example of successful use of PCMs in In the last decade, the general requirements to the
industry is the synthesis of phosgene (intermediate for the physicochemical state of carbon catalysts for various trans-
preparation of polyamides, polycarbonates, pharmaceuti- formations of organic compounds have been outlined
cals, etc.) from CO and Cl2 . Although this process has been (Table 1). There is the trend towards deliberate extension
known for more than 130 years, in 2000, DuPont published of the ranges of acid ± base, redox and electrophysical
Oxidative dehydrogenation of alkylarenes AC, CMS, MWCNT, filament carbon, micropores 0.5 ± 0.7 nm (plugged by
(ethylbenzene to styrene) with oxygen onion carbon, graphenes coke deposits); conjugated diketones
or quinone ± hydroquinone pair;
graphene edges
Oxidative dehydrogenation of alcohols AC, graphite oxide weakly acidic (phenolic)
to ketones or aldehydes with oxygen
Oxidation of methylbenzenes to aldehydes graphite oxide oxygen-containing redox groups
with oxygen
Oxidation of benzyl alcohol to benzaldehyde MWCNT p-electron system as the electron
with O2 + HNO3 donor ± acceptor
Oxidation of cyclic ketones (with ring opening) AC quinone ± hydroquinone pair
to dicarboxylic acids
Oxidation of benzene to phenol with H2O2 OC conjugated diketones
Total oxidation of organic impurities in H2O AC p-electron system as the electron
with H2O2 , O3 or O2 (mineralization) donor ± acceptor, O- and N-containing
basic sites
Dehydrogenation of alcohols AC Lewis acid and base sites
Dehydrogenation of propane AC basic sites
Hydrodechlorination nitrogen-doped PCM N-containing basic sites
Reduction of nitrobenzenes with sulfides AC quinone ± hydroquinone pair
or ethylbenzene
Hydrogenation of cyclohexene nitrogen-doped PCM based quinoline groups
on carbon black
Knoevenagel condensation, aldol AC from nitrogen-containing polymers, N-containing basic sites (pyridine)
condensation N-containing filament carbon
Hydration of alkynes graphite oxide acidic
Alcoholysis and aminolysis of epoxides, sulfonated coal strongly acidic groups (carboxy, sulfo
hydrolysis of esters, cellulose, alkylation groups)
=
at N7H groups, dimerization
=
of PhC(CH3) CH2
Dehydration of alcohols, transesterification, OC, sulfonated coal strongly acidic groups (carboxy,
esterification sulfo groups)
a AC is activated carbon (neutral or alkaline), OC is oxidized carbon (acidic), CMS is carbon molecular sieve, MWCNT are multiwalled carbon
nanotubes.
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 943
properties of PCMs by means of structure and surface The ability of carbon to absorb microwave radiation
modification with heteroatoms (B, N, Si, S, P, etc.), which opens up an alternative way of maintaining the temperature
are usually present in traditional carbons in low concen- of the reaction mixture. In addition, direct microwave
trations.576, 577 In addition, methods for the formation of heating of the catalyst can substantially increase the degree
chemical groups that are nearly absent in traditional ana- of conversion, while the contact time of the reaction mixture
logues (e.g., amino or sulfo groups) on the surface of novel and the catalyst decreases. For example, in the synthesis of
carbon catalysts are being developed. Generally, this period N-substituted g-lactams in an excess of aldehyde on the
was marked by high intensity of works on the use of PCMs Norit RX-1.5 Extra activated carbon doped with alkali
as catalysts to solve applied problems covering various metal ions (in particular, caesium ions, 0.08 mass %),
areas: environmental protection (detoxification and miner- short-term microwave irradiation (2450 MHz, 600 W,
alization of organic and inorganic compounds in industrial 5 min) of the reaction mixture at 115 8C resulted in a 70%
effluents and waste waters), alternative energy (production conversion at 100% selectivity, whereas with the reaction
of biofuels by vegetable oil transesterification), green chem- temperature being maintained by conventional heating,
istry (hydrolysis of biopolymers like cellulose and further only 50% conversion at 100% selectivity was reached over
processing of hydrolysis products into valuable chemical a period of 1 h (Scheme 140).
feedstock), polymer chemistry (monomer synthesis), fine Scheme 140
organic synthesis (manufacture of medical drugs, highly
selective catalysis in oxidation and condensation reactions, O O
coupling of steps in multistep processes, i.e., one-pot syn- O C5H11-n
Cs+/C
thesis). NH + C6H13-n N
108 ± 115 8C
The greatest number of publications are devoted to the H
use of sulfonated coals (C-SO 3H) (prepared by sulfona-
tion of activated carbons or their precursors by concen- Thus, the above examples provide new, rather convinc-
trated sulfuric acid) as heterogeneous acid catalysts, which ing evidence for the fact that carbon materials with the
often surpass in efficiency the known catalysts such as adequately adjusted physicochemical state of the surface
Nafion. 578 Cases in point are multistep processes involv- can catalyze complex organic reactions under fairly mild
ing more than two molecules, which can proceed on the conditions giving final products in nearly quantitative
sulfonated coal surface. An example is the synthesis of yields, as it is inherent in biological catalysts Ð enzymes.
spirooxindole derivatives Ð intermediates for the prepa-
ration of alkaloid-like drugs Ð by the Knoevenagel con- XI.2. Carbon materials as supports for the catalyst active
densation of isatin, malononitrile and 1,3-dicarbonyl component
compounds, the yields of target products being Processes catalyzed by metals and metal compounds sup-
80% ± 94% (Scheme 138).579 ported on carbon materials cover almost the whole spec-
trum of known catalytic reactions. Of course, it is
Scheme 138 impossible to consider them all. As examples, Table 2 lists
O O some organic reactions catalyzed by Group 8 metals or their
N R C-SO3H compounds supported on PCMs (M/C), while Table 3
+ + presents examples of processes catalyzed by efficient
O EtOH, D
O EWG
N Pd/Sibunit catalysts.
H In the discussion of modern organic synthesis problems,
O the attention is focused on the activation of unsaturated
NH2
=
C C and C:C bonds, the formation of new C7C bonds
R O EWG and oxidation reactions catalyzed by Group 8 metals
O supported on carbon nanotubes.
N
H XI.2.a. Supported M/C metallic catalysts
EWG = CN, CO2Et In M/C type catalysts used in organic synthesis, the content
of the active component is, most often, not higher than
One more example is the preparation of dihydropyrimi- 5 mass %. During the last decades, a vast number of
din-2(1H)-one (or -thione) derivatives by the Biginelli con- procedures have been proposed for targeted preparation of
densation of b-ketocarboxylic acid esters, aldehydes and supported catalysts with a desired degree of dispersion and
urea (or thiourea) (Scheme 139).580 The catalysts withstand pre-specified distribution of the active component over the
5 ± 6 cycles without loss of activity. PCM grain. Characteristic features and properties of these
Scheme 139 catalysts are described in a number of reviews.569, 581
H2N Apart from the development of methods for deposition
O O R0 H C-SO3H
+ + X of the active component, approaches to catalyst preparation
EtO R O H2N
140 8C by simultaneous formation of the support and the active
component have been developed. For example, nanoglobu-
O R0 lar carbon (the primary particles of this material are
spherical items 2 to 200 nm in diameter) is studied as a
EtO NH catalyst or catalyst support in liquid-phase reactions, espe-
R N X cially when they occur in microchannel reactors, as the
H absence of porosity and a great specific surface area
X = O, S promote increase in the activity by a large factor and
944 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
Reactions Metals
Pd Pt Ni Ru Rh Os
Isomerization + + + + + +
Reactions involving hydrogen
Dehydrogenation, dehydrocyclization and dehydroisomerization + + + + + +
Hydrogen addition at the C C and C:C bonds in aliphatic compounds
= + + + + + +
=
Hydrogenation of the C C bond in the ring or aromatic bonds + + + + +
=
Hydrogen addition at the C O bond + + + + +
Hydrogen addition at the C N and C:N bonds
= + + + +
Destructive hydrogenation with C7C and C7O bond cleavage + + + +
Destructive hydrogenation with C7N, C N, C:N and N:N bond cleavage
= + +
Reduction with molecular hydrogen with HHal release (Hal = Cl, Br, I) + +
Reduction of compounds containing NOH, NO and NO2 groups with H2O release + + + + +
Reductive cyclization +
Reductive condensation + + + +
Reduction with other agents (ammonia, cyclohexane, hydrazine, sodium borohydride, + + +
methanol, etc.)
Reactions involving CO (carbonylation, Fischer ± Tropsch reaction) + +
Reactions involving oxygen (oxidation of organic compounds) + + + + +
Catalytic processing of raw materials of complex composition
Oil hydrogenation and isomerization + + +
Rosin dehydrogenation and disproportionation +
Hydrogenolysis of heavy hydrocarbons +
Petrol aromatization +
Wood (lignin) hydrogenation +
Formation of new carbon ± carbon bonds + + + +
Polymerization
of diethylallylsilane, triallylsilane, etc. +
of di(silyl)- or di(vinylsilyl)arylenes +
of ethylene +
Electrochemical processes (catalysts for fuel cells) + + + +
Scheme 141
a
[Pd]
0 0
R X + RM R R + MX
=
R0 = Ar, All, Bn, CH CH2; M = Mg (Kumada reaction),
Sn (Stille reaction), Zn (Negishi reaction), B (Suzuki reaction)
Pd (metal)
Pd0 or PdII as
catalyst
the catalyst
deactivation
precursor
100 nm L
R R0 R0 X
Reductive Oxidative
L2Pd0
Figure 23. Photomicrographs of catalysts: 40% Pt/Sibunit 1562 elimination addition
(Ssp = 590 m2 g71) (a), 0.5% Pt/graphite (Ssp = 2 m2 g71) (b)
(authors' data). R0 L R0 R0
R Pd L R Pd R0 L Pd L L Pd X
L L X L
A number of effective procedures have been proposed
for the synthesis of Pt/C electrocatalysts by hydrolytic
and/or reductive deposition of platinum from H2PtCl6
solutions 590 and by additional formation of platinum bind- RM Transmetallation
ing sites on the PCM surface.589 In the latter case, the
resulting catalysts have a very narrow platinum particle size The homogeneous catalysts used in these reactions are,
distribution. A photomicrograph of a surface fragment of most often, palladium complexes: Pd(PPh3)4, Pd(PPh3)2Cl2,
such sample is shown in Fig. 23 a. It was shown experimen- Pd2(dba)3 and so on. Due to the increasing demand for
tally 587 that the efficiency of cathodes based on this catalyst valuable products obtained in this way, the development of
is close to that of the best commercial material, efficient heterogeneous analogues of cross-coupling cata-
40% Pt/Vulcan XC 72R ± Hispec 4000 (Johnson Matthey); lysts becomes a topical task. This would increase catalyst
however, the activity per unit weight is twice higher for stability, the problems of product separation would be
40% Pt/sibunit 1562 than for the commercial sample owing avoided and reuse of the catalyst would become possible.
to a higher degree of dispersion of platinum, which opens These catalysts can be fabricated, for example, by targeted
up the way for further advancement of electrocatalysts formation of palladium complexes directly on the surface of
based on Sibunit supports. carbon supports.592 Attempts are being made to attach
Methods for control of the platinum degree of disper- palladium complexes to polymers, gels or inorganic sup-
sion and particular size distribution developed for electro- ports, to use ionic liquids and so on.591, 592 However,
catalysts were successfully tested for the preparation and catalysts prepared in this way show lower activity.
regeneration of the 0.5% Pt/graphite catalyst (2 m2 g71) in
the synthesis of hydroxylamine sulfate by NO hydrogena- XI.2.c. Reactions involving oxygen
tion in sulfuric acid solutions (see Fig. 23 b), because the Due to the low corrosion stability of traditional carbon
surface concentrations of Pt particles in these catalysts are supports in oxidative atmosphere at elevated temperatures,
similar. the percentage of M/C catalysts promising for selective
oxidation of organic compounds has been rather low until
XI.2.b. Formation of new carbon ± carbon bonds recently. However, during the last two decades, quite a few
A special place in the modern organic synthesis is occupied publications dealing with the use of such catalysts for
by the reactions resulting in the formation of new C7C environmental protection processes appeared (the number
bonds. First of all, this is the palladium-catalyzed cross- of publications still increases).592, 593 For purification of
coupling reactions. One more way of forming C7C and liquids and gases from hazardous compounds (phenol,
C7X bonds (X is a heteroatom) in aromatic systems is organochlorine compounds, etc.), various combinations of
based on nucleophilic substitution of hydrogen. metals and their salts supported on carbon materials have
Reactions of the first type are couplings of organic been proposed. The percentage of studies devoted to the
halides with organometallic compounds in the presence of Au/C catalysts is growing.594, 595 The key applications of
Pd0 complexes (Scheme 141). these catalysts are related to oxidation of functional groups
946 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
oxidants (oxygen, hydrogen peroxide) and reductants conditions and development of a method for catalyst
(hydrogen), which would increase the selectivity of trans- regeneration. The process was commissioned in 1986 at the
formations and reduce the number of steps and amounts of EniChem Synthesis plant (Ravenna, Italy); in 2010, Camlin
industrial wastes. Fine Chemicals (India) became the owner of the production
A huge number of scientific publications are devoted to unit. The process changed little since the commissioning: the
various aspects of the use of heterogeneous catalysts for the oxidation is performed in an acetone, methanol and water
transformation of organic compounds, whereas information mixture at 80 ± 100 8C, the H2O2 : phenol ratio is 0.2 ± 0.3.
about the practical use of a particular catalyst for industrial For phenol conversion of 20% ± 30%, the selectivity to
organic synthesis processes is seldom encountered in pub- phenol is 90% ± 95%, that to hydrogen peroxide is
licly available literature. This is due to tough competition 80% ± 90%, and the pyrocatechol : hydroquinone ratio in
between chemical companies and to enormous expenses the phenol hydroxylation products is 1.1 ± 1.2. The annual
needed to develop the production process of one or another demand for hydroquinone is *55 000 tonnes and that for
chemical. This Section describes examples of relatively new pyrocatechol is *35 000 tonnes.
catalytic processes demonstrating advantages of the use of The process of propylene epoxidation with hydrogen
heterogeneous catalysts for oxidation and hydrogenation of peroxide was commissioned in 2001 at a pilot unit with
organic molecules in industrial organic synthesis. 2000 tonnes per year capacity belonging to the Eni group
(Ferrara, Italy). In the same year, the plant was purchased
XII.1. Heterogeneous catalysts in oxidative processes by Dow Chemical, which established a joint venture with
A successful example of application of heterogeneous cata- BASF in 2002 for commercialization of the process of
lysts in oxidative processes is the use of the titanosilicate propylene oxidation with hydrogen peroxide. Currently
TS-1-based zeolite material in the hydroxylation of phenol, this process is known as BASF/Dow HPPO (Hydrogen
epoxidation of propylene and ammoximation of cyclohex- Peroxide for Propylene Oxide), the propylene oxidation to
anone (in the presence of NH3) with hydrogen perox- propylene oxide (PO) being conducted in the presence of the
ide.600 ± 603 The works were started by the Eni company in TS-1 catalyst. The first industrial production of propylene
order to advance the process of hydrogen peroxide oxida- oxide by the new process with 300 000 tonnes per year
tion of phenol to give a mixture of hydroquinone and capacity was started in 2008 (Antwerp, Belgium). In Octo-
pyrocatechol (Scheme 143), which was previously carried ber 2011, propylene oxide production by the
out in the presence of an iron(II) and cobalt(II) salt mixture BASF/Dow HPPO process was started at a plant with
and had low efficiency, resulting in the formation of resins 390 000 tonnes per year capacity (Map ta phut, Thailand).
and non-optimal pyrocatechol : hydroquinone ratio The Evonic and Unde Gmbh companies also developed a
(2 ± 2.3). propylene oxide production process using hydrogen perox-
Scheme 143 ide. The process was implemented in South Korea (Ulsan);
OH OH OH a plant of 100 000 tonnes per year capacity was commis-
sioned in July 2008.604
OH
Comparison of the key characteristics of alternative
+
processes currently used to produce propylene oxide is
given in Table 4. The HPPO process, unlike the other two
OH catalytic processes, does not require organic peroxides
(ethylbenzene or styrene hydroperoxide); therefore, today
Screening of a large number of samples revealed a it is most environmentally attractive.602 Nevertheless, in
catalyst that exhibited high activity and selectivity in the 2009, only *8% of propylene oxide was produced in this
hydroxylation of phenol with hydrogen peroxide, namely, way, the rest being distributed approximately in equal parts
titanosilicate TS-1 [x TiO2 . (17x) SiO2, 0.0001 < x < 0.04]. among the non-catalytic chlorohydrin method and catalytic
The industrial application of this process was preceded by a methods using organic peroxides.600
long period of research aimed at the development of a Development of the catalytic process of cyclohexanone
reproducible method for the synthesis and commercializa- ammoximation in cyclohexylamine in the presence of tita-
tion of the catalytic material, optimization of oxidation nosilicate TS-1 formed the basis for environmentally
a Waste water treatment is required (for water and salt solution); b the yield was calculated in relation to the reagent.
948 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
friendly method for the production of caprolactam to be mann rearrangement) make use of heterogeneous catalysts.
used as the monomer for nylon 6. The conventional indus- To our knowledge, there are no other analogous processes.
trial methods for the manufacture of caprolactam start from Since the annual production of caprolactam is *4 million
cyclohexanone, which first reacts with an excess of an tonnes (data for 2010), the contribution of the heteroge-
aqueous solution of hydroxylamine sulfate at 0 ± 100 8C. neous catalytic process is < 2%.
In the second step, cyclohexanone oxime is converted to The patent and scientific literature describe examples of
caprolactam in the presence of sulfuric acid via the Beck- successful implementation of ketone ammoximation to give
mann rearrangement (Scheme 144). The production of products holding good prospects for commercialization.
caprolactam is accompanied by the formation of a large For example, ammoximation of p-hydroxyacetophenone
amount of the ammonium sulfate by-product (*4.4 kg per has been reported (Scheme 145), the resulting oxime being
kg of caprolactam); the synthesis of hydroxylamine com- the precursor of N-(4-hydroxyphenyl)acetamide (paraceta-
prises several steps and produces nitrogen oxide and sulfur mol).606, 607
oxide effluents. Scheme 145
Scheme 144
O OH
O N
+ NH2OH . H2SO4 + 2 NH3 H2O2, NH3
Me H+
Me
OH TS-1
N HO HO
H
N O
(NH4)2SO4 + H2O +
Me
OH HO
O
N Paracetamol
H2SO4 HN
The reaction selectivity is 100% for a 50% conversion of
the starting compound. The preparation of laurolactam, the
e-Caprolactam
monomer for nylon 12 production, has also been
reported.608, 609 No data on the industrial implementation
The reaction of cyclohexanone with ammonia and of these reactions are available.
hydrogen peroxide in the presence of the microspherical
TS-1 catalyst is free from by-products and gas effluents and XII.2. Catalytic methods for the reduction of organic
requires much less complicated equipment. It is commonly compounds
accepted that ammoximation involves hydroxylamine, It is impossible to describe the whole diversity of catalytic
which is formed in situ upon oxidation of ammonia with methods for the reduction of organic compounds within a
hydrogen peroxide in the presence of the TS-1 catalyst.603 single section; therefore, we will consider reactions that
The reaction with ammonia and hydrogen peroxide, result- proceed on Pd-containing catalysts and fall into the area
ing in cyclohexanone oxime and called ammoximation, was of research interests of the authors. It is known that
first performed by Lebedev and Kazarnovsky 605 in the palladium catalysts are used in numerous hydrogenation
presence of sodium tungstate. The possibility of process reactions;600 however, most active users of expensive cata-
commercialization was demonstrated on a pilot unit with a lysts are still pharmaceutical and defence industries.
capacity of 12 000 tonnes per year in 1994 at the Porto For example, the last step in the 10-step synthesis of
Marghera plant (Venice, Italy). The reaction was carried oseltamivir (antiviral drug efficient against the H5N1 bird
out in a flow type slurry reactor on a modified TS-1 flu virus) was implemented as reduction of the azide group
catalyst; cyclohexanone, ammonia and hydrogen peroxide to the amino group with hydrogen in the presence of the
were fed to the reactor in 1.0 : 2.0 : 1.1 molar ratio, the Pd/Sibunit catalyst (5% Pd/C) to give the necessary stereo-
reaction was carried out at 80 ± 90 8C with a tert-butyl isomer (Scheme 146). The industrial yield of the target
alcohol and water mixture as the solvent. Under these product was 63%; the use of highly active palladium
conditions, cyclohexanone was converted almost completely
(conversion >99.9%) to cyclohexanone oxime with >98%
selectivity. Scheme 146
Approximately at the same time, the Sumimoto com- Et Et
pany developed a heterogeneous catalyst for the Beckmann O CO2Et
rearrangement. In this process, cyclohexanone oxime reacts
in the vapour phase at a temperature of 300 ± 400 8C under
atmospheric pressure on a fluidized catalyst bed (MFI AcHN
zeolite). Upon optimization of the catalyst composition, it N3
was possible to reach a 95% selectivity towards caprolactam
Et Et Et Et
at a virtually complete conversion of cyclohexanone oxime.
Sumimoto purchased the license for hydroxylamine O CO2Et O CO2Et
production process and in 2003, commissioned the capro- +
lactam production unit with a capacity of 65 000 tonnes per
year at the Niihama plant (Ehime, Japan). In this process, AcHN AcHN
NH2 NH2
both steps (ammoximation of cyclohexanone and Beck-
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 949
catalyst resulted in reduction of the double bond, too, to quality are 2,6,8,12-tetraacetyl-4,10-diformyl-2,4,6,8,10,12-
give the side product.610 hexaazaisowurtzitane (TADF) and 2,6,8,12-tetraacetyl-
Naloxone, naltrexone and its derivatives are opioid 2,4,6,8,10,12-hexaazaisowurtzitane (TA).
receptor antagonists used to treat narcotic and alcohol In the two-step catalytic debenzylation, a catalyst con-
addictions. Carbon-supported palladium is used to prepare taining 5% ± 10% palladium on carbon and bromobenzene
intermediates for the synthesis of naloxone and naltrexone as the co-catalyst are used.
and for the synthesis of naltrexone derivatives Scheme 149
(Scheme 147).611 Bn
Bn Bn
Scheme 147 N
N Ac2O, H2, Pd/C
N
HO HO PhBr, DMF
N
N N
a b Bn Bn
O O HB Bn
N N
OH OH Ac Ac
R Bn
O N N N
Naltrexone N H2, Pd/C
Bn
HO N
N N Ac
Bn
TADB Ac
O
N OHC Ac Ac
N N
OH HCO2H N
R
N
H N
N N
OHC Ac
R = H, Me, CH2CH2OH, Et, Bun;
TADF Ac
(a) HNBnR; (b) H2 (1 ± 2 bar), 10% Pd, AcOH
Ac Ac
HN N
In the six-step pilot procedure for the synthesis of AcOH N
estetrol, a versatile hormonal agent, the benzyl and acetyl
groups are used to protect the active hydroxy groups. N
HN N
Deprotection is accomplished in the final step of the syn- Ac
thesis. First, O-debenzylation is carried out and then the TA Ac
acetyl group is removed by alkaline hydrolysis under mild
conditions (Scheme 148).612 The catalyst is employed successively in two debenzylation
Scheme 148 steps, the key problem faced by the practical implementa-
O tion of these steps being fast catalyst deactivation. The
known methods for regeneration of heterogeneous catalysts
do not restore the activity to the initial level, which
...
precludes repeated use of the catalyst. From the spent
catalyst, palladium is isolated and used to prepare the new
HO OAc
catalyst. The cost of the palladium catalyst can amount to
1) H2, 10% Pd/C 35% ± 40% of the HNIW prime cost. Therefore, lots of
OH
2) K2CO3 studies have been devoted to the search for catalytic systems
that would allow repeated use of the expensive catalyst.
OH
BnO
Using the modern industrial production of HNIW, we
OH will consider the scope and limitations of the catalytic
chemistry for solving industrial problems. The industrial
OH production process of this compound with a capacity of 5 to
100 tonnes per year is demanded for solution of important
OH practical problems. An attempt of repeated use of the
HO palladium catalyst in the step of 2,4,6,8,10,12-hexabenzyl-
Estetrol 2,4,6,8,10,12-hexaazaisowurtzitane (HB) debenzylation has
been patented.616 It was shown that some commercially
The most widely used large-scale industrial process available Degussa catalysts used in the two-step reductive
involving palladium catalysts in industry is the production debenzylation of HB (Scheme 150) can be reused (see
of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzi- Scheme 149, HB ? TADB ? TADF). However, in the sec-
tane (HNIW, CL-20). This is a promising and powerful ond catalyst cycle, the yield of 2,6,8,12-tetraacetyl-
explosive Ð a component of explosive formulations and 4,10-dibenzyl-2,4,6,8,10,12-hexaazaisowurtzitane (TADB)
composite solid propellants.613, 614 The key step of the considerably decreases and subsequently tends to zero.
HNIW preparation is Pd-catalyzed reductive debenzylation A method for TA preparation with repeated use of the
(Scheme 149).615 The most convenient starting compounds catalyst containing up to 10% palladium (see Scheme 150)
the nitrolysis of which gives the best yields and product has been described in patents.617, 618 When ten debenzyla-
950 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
Scheme 150
catalyst recycling
Bn Bn Ac Ac Ac Ac Ac Ac
Bn Bn Bn HN
N N N N N
N N N
N Ac2O, H2, [Pd] N N N H2O
+ +
DMA H2, [Pd]
N N N N
N N N N N N N N
Bn Bn Bn Ac HN Ac HN Ac
HB Bn Ac Ac Ac
TADB (64%) (11%) TA (9%)
Ac Ac
HN
N N
N
N
N N
HN Ac
TA Ac
tion runs were performed, the TA yield was not less than Table 5. Use of bimetallic catalysts in the synthesis of tetraacetyldi-
80% in each step. This debenzylation method formed the formyl hexaazaisowurtzitane.622
basis of an industrial process for the synthesis of HNIW.617
Catalyst [metal TADF yield (%)
However, this process proved to be of low utility for the content (%)]
preparation of the diformyl derivative (TADF), used most freshly prepa- 1st recycle 2nd recycle
often in HNIW synthesis. red catalyst
Studies of the catalytic debenzylation ± formylation step
(HB ? TADB ? TADF) have been reported.619, 620 The Pd/C (6) 69 0 0
studies concerned the effects of the preparation procedure Pd/C (10) 75 0 0
of heterogeneous catalysts, components of the reaction Pd : Ir/C (6 : 3) 76 70 59
mixture and process conditions on the catalyst stability Pd : Pt/C (6 : 3) 72 73 0
against deactivation in the catalytic debenzylation. Using Pd : Pt : Ir/C (6 : 1.5 : 1.5) 60 51 22
modern methods of analysis, the authors established the Pd : Ir/C (4 : 3) 0 0 0
optimal degree of dispersion of Pd on the support surface Pd : Ir/C (6 : 1) 73 0 0
for debenzylation. It was shown that in the two-step Pd : Ir/C (6 : 4) 72 67 55
catalytic debenzylation, redistribution of palladium par- Pd/C (6) + Ir/C (3) 69 0 0
ticles on the carbon support takes place and the particle Pd : Ir/CFC (6 : 3) a 70 66 50
size markedly increases. The researchers concluded that the
a CFC is catalytic fibrous carbon.
decrease in the Pd/C activity is due to plugging of the
metallic palladium in the support pores by the by-products
resulting from oligomerization of intermediates and to
agglomeration of metal particles. to enhancement of the catalyst stability against deactiva-
A known method for increasing the stability of palla- tion. However, the overall yield of TADF per gram of the
dium metal particles in the Pd/C catalysts is introduction of catalyst remained rather low.
the stabilizing metal into the catalytic system.621 Stabiliza- Proceeding from the assumption that the use of the
tion can be attained due to both the electronic effect catalyst only in one debenzylation step stabilizes the cata-
(change in the electronegativity of the active metal) and lyst operation, a process chart for separate use of the
modification of the carbon support surface. catalyst was proposed (Scheme 151).623 ± 625 The data pre-
A patent 622 describes a series of bimetallic systems that sented in Fig. 25 illustrate the possibility of repeated use of
were tested in the two-step hydrodebenzylation reaction the catalyst containing 5.6% ± 5.9% palladium in the first
(HB ? TADB ? TADF). Particular attention was paid to debenzylation step (HB ? TADB).
the possibility of conducting the second hydrodebenzylation The second debenzylation step is less sensitive to the
cycle (recycle) with spent catalysts. According to the results quality and morphology of the catalyst. When the process
presented in Table 5, the addition of stabilizing metal ions employs the reused catalyst, the TADF yield decreases
during the catalyst preparation resulted, in some cases, in noticeably only in the 14th cycle. Also, the catalyst that
increased catalyst productivity for the target product owing has already served for ten cycles in the first step was able to
Scheme 151
Bn Bn Ac Ac OHC Ac Ac
Bn Bn
N N N N N
N N HCOOH N
N Ac2O, H2, Pd/C
PhBr, DMF Pd/C, H2
N N N
N N N N N N
Bn Bn Ac OHC Ac
Bn
HB Bn TADB Ac TADF Ac
90 12
2
Yield of TADB (%)
10
70
50 6
1
4
30
1 2 3 4 5 6 7 8 9 10 11 12 2
Cycle number
0 2 4 6 8 10 12 14
Cycle number
Figure 25. Yield of TADB upon repeated use of Pd/C cata-
lyst.623, 625 Figure 27. Change in the palladium particle size upon repeated use
(1) Hydrogenation at Pg = 2 ± 5 kg cm72 for 6 h, (2) hydrogenation of the Pd/C catalyst.623, 625
at Pg = 0.05 kg cm72 for 18 h. (1) HB ? TADB, (2) TADB ? TADF.
Freshly prepared
catalyst
A mixture of TADB + cat: a TADB solution
catalyst separation and after 2 operations
Step 1: TADB in step 1 Step 2: TADF Catalyst separation,
washing, preparation of a
preparation preparation isolation of TADF
solution of TADB in a
HCO2H + AcOH mixture
10 cycles 5 cycles
ibuprofen, an anti-inflammatory drug (annual production of 35% hydrochloric acid and 100 tonnes of sodium
of about several thousand tonnes), included seven steps hydroxide annually in the initial sertraline production
(Scheme 152), the yield in each step being lower than 100%, process.
which gave rise to huge amounts of diverse wastes (acetic Scheme 154
acid, ethyl chloroacetate, hydroxylamine). O NMe
Scheme 152
MeNH2 H2, Pd/CaCO3
HCl, AcOH,
Al wastes HCl EtOH EtOH
Bui Bui Cl Cl
Cl Cl
K+B7 Ac2O ClCH2CO2Et
+ +
AlCl3 NaOEt NHMe NHMe NH2Me
AcOH
O D-Mandelic Cl7
acid HCl
Bui Bui Bui
EtOH EtOH
H+ NH2OH
H2O 7H2O Cl Cl Cl
Cl Cl Cl
HON
EtO2C OHC Sertraline
O
hydrochloride
Bui Bui
The presented examples demonstrate the efficiency of
H+
using heterogeneous catalysts in industrial production of
H2O
organic compounds. The increase in cost efficiency (higher
yield, fewer number of steps, no protecting groups, simpler
HO2C isolation, lower material consumption) and environmental
N
Ibuprofen safety (lower amounts of wastes and effluents, replacement
of toxic reagents by catalysts) in industrial organic synthesis
According to the new process developed by the Hoechst- processes stimulates commercialization of catalytic reac-
Celanese company, ibuprofen is produced in two catalyzed tions. This is promoted by development of new catalytic
steps Ð hydrogenation and carbonylation (Scheme 153). As materials (supported mono- and bimetallic nanoparticles,
a result, the amount of wastes per 206 kg of ibuprofen grafted metal complexes and enzymes) able to catalyze
decreased from 308.5 to 60 kg, acetic acid being the only by- selective transformations of complex organic molecules.
product. Apart from extension of the use of heterogeneous catalysts,
Scheme 153 modern trends of organic synthesis include the implementa-
AcOH tion of flow type reactors, attempts to use supercritical
carbon dioxide and ionic liquids as solvents and intensifi-
Bui Bui Bui Bui cation of organic reactions upon physical action on the
reaction mixture (ultrasound, microwave radiation).600, 604
HF H2, Ni Co, Pd
In the 20th century, heterogeneous catalysts were
Ac2O
actively introduced mainly in large-tonnage production
processes of fuels and semi-products at large plants. The
O HO HO2C goal for the 21st century is the development and commerci-
alization of heterogeneously catalyzed processes in fine
Ibuprofen
organic synthesis.
The antidepressant drug sertraline was initially pro- XIII. Studies of the mechanisms of catalytic
duced over three steps, each using a different solvent, with reactions by the nuclear spin hyperpolarization
intermediate isolation of products of each step.600, 604
In the new process developed by Pfizer, the three steps
technique
are performed in the same solvent, ethanol, and no isolation The immense potential of heterogeneous catalytic reactions
of the intermediate products between the steps is required and high demand for heterogeneous catalysts in fine organic
(Scheme 154). The yield of the final product increased synthesis determine the increasing interest in the research in
twofold (to 37%) and ethanol replaced toluene, tetrahydro- this area. However, a serious obstacle comes from the
furan and hexane solvents, the total solvent consumption considerable complications in the studies of reaction mech-
was reduced from 240 to 24 litres per gramme of the anisms caused by specific nature of heterogeneous systems
product. In addition, implementation of this process (see Section IX). It is the development of new methods for
makes it possible to avoid the large amount of wastes, investigation of mechanisms of complex catalytic reactions
which was up to 440 tonnes of titanium dioxide, 150 tonnes that will predetermine the progress in this area for selective
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 953
organic synthesis. A highly interesting investigation method add to a substrate molecule, the symmetry of the initial H2
for reactions involving molecular hydrogen (see Section- molecule disappears, which may result in a pronounced
s IX ± XII) is the nuclear spin hyperpolarization method enhancement of NMR signals owing to the so-called para-
considered in this Section. hydrogen induced polarization (PHIP).
Molecular hydrogen (H2) has two nuclear spin isomers, The PHIP effect was first demonstrated in the hydro-
orthohydrogen and parahydrogen, which are chemically genation of acrylonitrile to propionitrile.642 Since then, this
identical but differ by a number of physical properties. approach has been widely used to study the mechanisms and
Therefore, physical methods (e.g., heat capacity measure- kinetics of homogeneous processes in solution, which
ment) can be used to determine their ratio in the mixture. In include the step of H2 activation by transition metal com-
the equilibrium state at room temperature, hydrogen exists plexes.643, 644, 646 ± 648 Owing to the high sensitivity of NMR
as a 3 : 1 mixture of ortho- and para-isomers. A relatively in combination with PHIP and the unusual line shapes in
simple procedure can be used to produce various degrees of the spectra (the presence of antiphase multiplets or signals
parahydrogen enrichment of H2 up to almost pure para- with different signs), these experiments can provide a lot of
hydrogen. In the 1930s, parahydrogen was actively used to information about hydrogenation reactions. Therefore, of
study the mechanisms of heterogeneous catalytic proc- considerable interest is to extend the PHIP technique to
esses.629, 630 It is well known that hydrogen can be dissocia- heterogeneous catalytic processes. However, this area has
tively chemisorbed on contact with the surface of a remained unexplored until recently, mostly, due to the belief
catalytically active metal. Upon the subsequent recombina- among specialists that heterogeneous hydrogenation proc-
tion of the pairs of random H atoms on the surface, the esses cannot preserve the molecular nature of H2 upon
ortho- and para-isomer ratio for the resulting H2 molecules addition to the substrate, i.e., two hydrogen atoms of the
is equal to the thermodynamically equilibrium ratio for the same H2 molecule cannot end up in the same product
given temperature. Therefore, upon metal activation, para- molecule due to the specific character of reaction mecha-
hydrogen is converted to an equilibrium mixture of ortho- nism on metal catalysts. Since pairwise addition of H2 is
and para-isomers. The rate of this transformation is necessary for the PHIP effect to arise, there was the opinion
believed to be a direct measure of the H2 dissociation rate that PHIP cannot be observed in heterogeneous catalytic
on the catalyst surface.631 Thus, comparison of the rates of reactions. Only in 2007 ± 2008, it was demonstrated exper-
reactions of substrate with H2 and D2 , the H2 + D2 ? 2 HD imentally that heterogeneous catalysts, including supported
exchange rate and the ortho ± para hydrogen conversion metal catalysts, are able to add hydrogen to multiple bonds
rate provides important information about the mechanisms of unsaturated substrates in the pairwise fashion and give
of H2 activation and chemical transformations in heteroge- rise to PHIP effects.649, 650 Since then, the PHIP technique
neous hydrogenation processes.630 ± 632 has been developed as a highly sensitive tool for studying
In combination with the NMR technique, parahydrogen not only homogeneous but also heterogeneous hydrogena-
provides even more useful and diverse information on tion processes. This Section briefly outlines the recent
catalytic processes. Analytical methods based on NMR advances in this research area.
have become an indispensable tool for numerous advanced
applications in physics, chemistry, biology and medicine. XIII.1. The use of parahydrogen to study the catalytic
For example, NMR spectroscopy is widely used in modern hydrogenation processes
chemical investigations, in particular, to study the mecha- As has already been noted, the PHIP effect is widely used to
nisms of homogeneous 633 and heterogeneous 634 ± 637 cata- considerably enhance the NMR signal in the studies of the
lytic reactions by detecting the reaction intermediates and mechanisms and kinetics of reactions in which molecular
products, dynamic processes involving them, reaction hydrogen is activated by metal complexes in solu-
kinetics and so on. The spatially resolved NMR technique tion.643, 644, 646 ± 648 The observation of PHIP for NMR
(NMR imaging, MRI), which has acquired wide use in signals of hydrogenation products usually attests to pair-
medical diagnosis and biological studies on animals, is also wise addition of hydrogen to the substrate, which, in the
successfully used in chemical engineering and catalysis, in case of mononuclear metal complexes, implies homolytic
particular for in situ and operando studies of catalytic hydrogen activation by the catalyst to give an intermediate
reactions and reactors.638 However, a factor that impedes dihydride complex. Conversely, monohydride complexes
further extension of the scope of applicability of NMR is perform non-pairwise addition of hydrogen (i.e., two H
low sensitivity caused by a small difference between the atoms that end up in the same product molecule have
populations of energy levels of nuclear spins in the magnetic belonged previously to different H2 molecules), and no
fields of modern NMR and MRI instruments. Therefore, in PHIP appears. In some cases, the observation of PHIP
recent years, considerable attention in NMR has been paid served to identify the true dihydride nature of the catalyti-
to development of the methods of nuclear spin hyperpola- cally active complex, although a monohydride complex is
rization, which can increase the intensity of NMR signals by used as the precursor.651 The PHIP effect can also help to
3 ± 4 orders of magnitude or even more.639 ± 641 One of these distinguish between the hydrogen atoms that were inherited
approaches is based on the use of parahydrogen in catalytic from the substrate and those that came from H2 in the
hydrogenation of unsaturated organic compounds.642 ± 645 product molecule. In particular, in the hydrogenation of
From the NMR standpoint, a significant difference alkynes, it is possible to distinguish between the syn- and
between the hydrogen spin isomers is the different value of anti-addition of hydrogen even if the resulting alkenes are
the total nuclear spin of the H2 molecule, which is 1 for chemically identical (for example, in the hydrogenation of
orthohydrogen and 0 for parahydrogen. Thus, the para- propyne or but-1-yne to the corresponding alkenes). For
hydrogen molecule itself does not produce a 1H NMR conjugated dienes, this can be used to identify processes
signal. However, H2 enriched in the para-isomer shows a such as 1,4-addition.652 In the hydrogenation of styrene
high degree of nuclear spin correlation. As both H atoms catalyzed by some cationic rhodium complexes, polarized
954 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
ment of the complex from the support. Reactivation unsaturated hydrocarbons. For propyne hydrogenation
of the catalyst at higher temperatures is caused by over the Pt/g-Al 2 O 3 catalyst, propylene was shown to
partial reduction of the complex. 666 be formed upon both syn- and anti-addition of hydro-
The behaviour of some immobilized iridium com- gen atoms to the triple bond. Similar non-stereoselec-
plexes has also been studied. Indeed, with Vaska's tive addition of hydrogen was observed also in the
complex [IrCl(CO)(PPh 3 ) 2 ] immobilized on silica gel, hydrogenation of but-1-yne to but-1-ene. 645 In this
substantial levels of conversion in the gas-phase reaction, PHIP was also observed on but-2-ene (cis-
hydrogenation of propylene were achieved; however, and trans-isomers) and butane. The same products
the PHIP effects were minor. The same catalyst were detected upon buta-1,3-diene hydrogenation. In
provided substantial (*10 2 -fold) enhancement of the both cases, the appearance of PHIP allowed research-
NMR signal of propylene in the hydrogenation of ers to propose the reaction scheme for the pariwise
propyne at 110 8C but at low conversion levels. hydrogen addition. It is noteworthy that PHIP effects
While recording the magic angle spinning NMR spec- were much higher for metal nanoparticles supported
tra, the PHIP effect was detected not only for propy- on TiO 2 .
lene in the gas phase but also for propylene adsorbed The PHIP formation is structurally sensitive. The
on a porous catalyst. This catalyst remained stable in influence of the platinum particle size on the PHIP
a hydrogen atmosphere even at 140 8C. Other immo- has been studied in detail for propylene hydrogenation
bilized catalysts based on iridium have also been catalyzed by Pt/g-Al 2 O 3 with various metal particle
studied. Some of them produced up to 400-fold sizes. 673 The dependence of the magnitude of PHIP on
enhancement of the NMR signal; however, the cata- the particle size proved to be non-monotonic: the
lysts were deactivated in several minutes under the effect was least pronounced for particles of diameter
reaction conditions. 2 ± 4 nm and increased for both larger and smaller
Supported ionic liquids can be used as an alter- particles (Fig. 30). The most pronounced effect was
native approach to immobilization of metal complexes observed for the smallest metal particles (<1 nm).
on a porous support. Catalysts based on supported Based on analysis of the data, it was concluded that
ionic liquids are successfully used in various catalytic the pairwise addition of hydrogen catalyzed by par-
reactions, in particular, hydrogenation. 667, 668 Attempts ticles of <3 nm size occurs predominantly on low-
to use these catalysts for hydrogenation of unsatu- dimensional sites, e.g., kink or corner Pt atoms,
rated compounds with parahydrogen have been whereas for larger particles, the pairwise addition
reported. In the presence of a cationic rhodium com- occurs on polyatomic active sites. The major reaction
plex dissolved in an ionic liquid supported on silica channel is non-pairwise, being accomplished on active
gel, hydrogenation of propylene was accompanied by sites of the most close-packed faces of metal particles.
substantial PHIP effects on propane.669 However, the Similar dependences of PHIP on the nanoparticle size
catalyst showed unstable behaviour with time, which were elucidated for Pt on ZrO 2 and SiO 2 . A different
is likely due to reduction of the complex at elevated result was obtained in analysis of the structure sensi-
temperature to give metal particles. The possibility of tivity for buta-1,3-diene hydrogenation on
this reduction in situ has been confirmed. 670 In the Pt/g-Al 2 O 3 . 645 In this case, both the major reaction
organic phase ± ionic liquid two-phase system, hydro- channel and the pairwise addition of hydrogen were
genation of ethyl acrylate on a cationic rhodium associated with the active sites located on flat nano-
complex showed no PHIP effects. 671 particle faces.
One more example of observing PHIP with a metal Palladium-based catalysts are known for their abil-
complex immobilized on a porous support is the use ity to perform selective partial hydrogenation of
of Au III Schiff base complex attached to a metal-
organic coordination polymer. 672 Hydrogenation of
H
propylene and propyne at 130 8C did not result in 1 cat
+ H2 H
catalyst deactivation and allowed for observing PHIP 4
3 2 5
effects on propane and propylene, respectively; pro-
pyne hydrogenation to propylene proceeded stereose- 11.5
lectively as syn-addition of hydrogen atoms. 6.5
It has been considered for a long period of time 3.8
that hydrogenation according to the Horiuti ± Polanyi 2.2
1.3
mechanism rules out the pairwise addition of hydro- <1 nm
gen to a substrate and, hence, the PHIP effect for
1 2 3
metal catalysts should be impossible. Nevertheless, it Propy-
was demonstrated 650 that PHIP can be observed in 4 lene + H2
hydrogenation of unsaturated compounds with para- Catalyst
hydrogen on supported metal catalysts. While using 5
Pt/g-Al 2 O 3 catalysts with a metal particle size of
0.6 ± 8.5 nm, a considerable PHIP effect on the reac- 6 4 2 0 d /ppm
tion product, propane, was detected, being most pro-
nounced for the metal particle size of 0.6 nm. The Figure 30. 1H NMR spectra recorded during hydrogenation of
particle size effect in this reaction was later studied in propylene with parahydrogen over the of Pt/g-Al2O3 catalysts
more detail (see below). Subsequently, it was shown with different metal particle size.673
that PHIP also arises in the hydrogenation of other
956 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
the propyne hydrogenation, PHIP was observed for An important open question related to the forma-
propylene but was nearly absent for propane although tion of PHIP on heterogeneous catalysts is the nature
the latter formed in substantial amounts. Since the of the active sites able to perform the pairwise
hydrogenation of propyne catalyzed by reduced cata- addition of hydrogen to multiple bonds. For metals,
lysts is non-stereoselective, while that catalyzed by the rate of diffusion of hydrogen atoms on the surface
immobilized complexes leads mainly to syn-addition is so high that in the absence of additional restric-
of hydrogen to the triple bond, this can serve as the tions on the mobility of newly chemisorbed hydrogen
criterion to verify the stability of immobilized com- on the surface, the probability of pairwise addition
plexes in hydrogenation reactions with parahydrogen. should be very low. The initial interpretation of PHIP
Chitosan-supported Rh nanoparticles were used in the on supported metal catalysts was based on the
hydrogenation of buta-1,3-diene and but-1-yne in the assumption of the existence of static or dynamic
gas and liquid phases. 675 The catalysts showed selec- partitioning of the metal surface into small islands
tivity towards the formation of but-1- and but-2-enes due to the presence of various sorts of adsorbates. 650
and provided PHIP effects. The Rh/TiO 2 and Rh/ This may result in localization of active sites upon
AlO(OH) catalysts demonstrated PHIP effects for formation of obstacles to free diffusion of hydrogen
dissolved propane in the liquid-phase hydrogenation across the metal surface. The existence of numerous
of propylene 645, 676 and in the hydrogenation of styr- surface structures such as carbonaceous depos-
ene to ethylbenzene in acetone. 676 Substantial PHIP its, 679 ± 681 reaction intermediates and side low-activity
effects were observed in the hydrogenation of methyl species 682, 683 in hydrogenation reactions is well-
propiolate to methyl acrylate in methanol catalyzed by known. However, other explanations can also be
Pd/SiO 2 , Pt/SiO 2 and Pt supported on mesoporous proposed. For example, for supported metal catalysts,
materials, Al- SBA-15 and Al-MCM-48, and in hydro- several types of active sites operating in parallel can
genation of styrene and phenylpropyne catalyzed by simultaneously exist, and some of them may be able
Pt/SiO 2 . 677 to perform the pairwise addition of hydrogen to the
A key issue in the investigation of PHIP is to substrate. These sites can be represented by some low-
estimate the contribution of the pairwise hydrogen dimensional structures such as corners, edges and
addition channel to the overall hydrogenation mecha- some faces of metal nanoparticles and the interfaces
nism. This information is necessary for understanding between the metal and the support. For supported
of the pairwise addition mechanism and for the search metal catalysts, the support surface may bear not only
for ways to attain the maximum PHIP-induced metal nanoparticles but also other active phases
enhancement of the NMR signal with the use of (metal oxide, single metal atoms and so on). A
heterogeneous catalysts. These estimates were made fundamentally different possibility is participation of
based on comparison of the theoretically calculated molecular hydrogen in hydrogenation, when an H 2
maximum possible enhancement of the NMR signal molecule (possibly physisorbed) reacts with the
when parahydrogen is used in the reaction and the adsorbed substrate molecule without dissociative
experimentally measured enhancement of the 1 H NMR chemisorption of hydrogen.
signal of the reaction products. 645, 664 This method is As noted above, metal oxides used as the supports
likely to underestimate the contributions of the pair- for the production of finely dispersed supported metal
wise addition, because some polarization is inevitably catalysts can have a pronounced influence on the
lost due to nuclear spin relaxation effects between the activity and selectivity of these catalysts. Furthermore,
instants of formation and observation of the polarized many oxides exhibit the catalytic activity themselves.
reaction products. Nevertheless, even this lower-bound From the standpoint of development and application
estimate of the pairwise contribution appears quite of the PHIP technique, of interest is the activity of
useful. some oxides in heterogeneous hydrogenation of unsa-
For propylene hydrogenation to propane catalyzed turated compounds.
by Pt/g-Al 2 O 3 with metal nanoparticles of 0.6 nm size, Hydrogenation using metal oxides has a number of
the contribution of the pairwise route was estimated distinctive features. For example, the rate of hydro-
as *3%. 650, 664 A similar value (*2.4%) was also genation of conjugated dienes is often higher than the
found for the Pt/TiO 2 catalyst with Pt particle size rate of alkene hydrogenation. Indeed, hydrogenation
of 0.7 nm. 673 For most of other catalysts, substrates of buta-1,3-diene catalyzed by alkaline earth metal
and experimental conditions, lower values were found. oxides occurs at 273 K to give butenes rather than
This implies that the metal-catalyzed addition of butane, whereas butene hydrogenation becomes signif-
hydrogen to the substrate is mainly non-pairwise, icant only at 473 K. 684 The reaction proceeds mainly
which is generally consistent with the Horiuti ± Polanyi as 1,4-addition of hydrogen atoms to buta-1,3-diene
mechanism. In another work,678 owing to the use of to give but-2-enes, whereas using metal catalysts, but-
4-sulfanylbenzoic acid for stabilization of the sup- 1-ene resulting from 1,2-addition is formed as the
ported Pt nanoparticles, higher percentages of pairwise major product. Finally, many researchers point to
addition in the propylene hydrogenation to propane retention of the molecular identity of hydrogen
may have been achieved. However, the authors made atoms in the reaction, i.e., they point out that two
an experimental mistake; therefore, the actual percent- hydrogen atoms that have ended up in the same
age of pairwise addition is unknown for these experi- product molecule belonged to the same H 2 molecule
ments. In addition, the use of the sulfur-containing before the reaction. 685 As noted above, this is crucial
ligand considerably lowered the yield of the reaction for the formation of the PHIP effect for the products
product. (and intermediates). Therefore, one could expect that
958 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
addition of hydrogen to the substrate. The under- tion of biologically active compounds and applications
standing of this mechanism should form the grounds of organic synthesis to solve problems of pharmaceut-
for the design of catalytic systems capable providing ical and biomedical chemistry are considered in Sec-
an extra 30-100-fold NMR signal enhancement com- tions II ± XII. Yet another highly practically important
pared to the values attained to date. Besides, this application of fine organic synthesis is the fabrication
would enable more rational utilization of the PHIP of molecular building blocks for the design of a new
technique to study the mechanisms of heterogeneous generation of smart materials. The most interesting
catalytic reactions, including not only hydrogenation trends in this area are briefly considered in Sections
but also other catalytic processes important from the XIV and XV.
industrial standpoint. Owing to the development of organic synthesis,
The achievements and the potential of the PHIP since the beginning of the 21st century, organic
technique are quite significant. However, the use of electronics has been actively developed based on the
parahydrogen has a number of limitations. In partic- ability of some p-conjugated oligomers and polymers
ular, the method requires that hydrogen participates in to conduct electrical current and to exhibit semicon-
the reaction in question, while the necessary condition ductor and luminescence behaviour. 690, 691 These com-
of pairwise addition of two hydrogen atoms of the H 2 pounds are prepared, as a rule, by forming aryl or
molecule to the substrate is in conflict with fast hetaryl C7C bonds using organometallic reactions.
migration of hydrogen atoms on the metal surface The enormous progress in this area is, beyond
after H 2 dissociation. Therefore, to understand the doubt, related to advances of organic and organo-
PHIP mechanism, it is important to theoretically metallic synthesis, which may provide diverse and
study the H 2 activation processes on metals and the more and more complex conjugated compounds with
subsequent fate of hydrogen atoms under reaction predetermined chemical structure and with control
conditions with allowance for lateral interactions of over molecular-mass characteristics, solubility and
adsorbed species. Yet another promising line of devel- morphology of conjugated polymers. It is also neces-
opment of this area is the use of nuclear spin isomers sary to do justice to the design of new devices based
of other molecules. However, to produce them in on these compounds and new methods for fabricating
amounts sufficient for NMR is a complex scientific them, which is a necessary condition for the develop-
and technological problem which remains unsolved. 688 ment of this area. 692, 693 This Section deals with the
Nevertheless, it was demonstrated experimentally for chemical aspects of this area related to the achieve-
the first time 689 that nuclear spin polarization can be ments and prospects of using organometallic synthesis
generated by using nuclear spin isomers of the ethylene for the preparation of p-conjugated oligomers and
molecule for which isomer enrichment was accom- polymers for organic electronics. Among such reac-
plished by chemical synthesis (hydrogenation of normal tions, one can distinguish four key types used most
acetylene with parahydrogen). widely and giving the best results. These are Suzuki,
The methods for signal enhancement by nuclear Kumada and Stille reactions and, in recent years,
spin hyperpolarization become highly demanded in a direct C7H arylation. Below these reactions are
variety of NMR and MRI applications, including considered in more detail using numerous particular
biomedical ones. Indeed it has already been demon- examples.
strated that this approach is highly promising in the
studies of metabolic processes in a living body on a XIV.1. Selective catalytic reactions for the preparation of
real time basis by introducing hyperpolarized com- organic semiconductors and luminophores
pounds into the body and observing the products of XIV.1.a. Application of the Suzuki reaction
their metabolism. 640, 641 This opens up new, in princi- The key advantages of the Suzuki reaction include the
ple, possibilities for early diagnosis of various pathol- almost complete absence of undesirable side reactions,
ogies, including cancer, and early detection of response due to the fact that the boronic acid residues cannot
to therapy. A recipe for success in the development of be exchanged with a halogen atom, and high yields of
biomedical applications of PHIP is obviously transition the reaction products (see Sections VI.2 and X.2). The
from homogeneous to heterogeneous catalysis to imple- absence of heavy elements, apart from palladium,
ment the possibility of obtaining solutions of hyper- makes this approach suitable for the synthesis of
polarized contrast agents containing no dissolved compounds of various classes used to fabricate devices
catalyst. Thus, biomedical applications form a power- for organic electronics. For example, the Suzuki reac-
ful impetus for the development of the PHIP technique tion served to prepare a number of polymers 694, 695
based on heterogeneous catalysis. and star-shaped oligomers 696 ± 698 for photovoltaic
cells, linear 699, 700 and star-shaped oligomers 701 for
XIV. Preparation of materials for organic thin-film field effect transistors, dendrimers for pho-
tonics 702 ± 705 and materials for monolayer field effect
electronics transistors.706 By selecting appropriate catalytic sys-
The preceding Sections considered issues of the stra- tems, polymers possessing both p-type (hole conduc-
tegic progress of organic synthesis and elaboration of tion) 707, 708 and n-type (electron conduction) 709 semi-
new synthetic methods. For correct analysis of the conductor properties have been prepared by pseudo-
prospects for the development of this area, it is also living polymerization. The polymers had a narrow
necessary to take into account the demands of the molecular-mass distribution and controlled terminal
modern research and production complex and the groups, which is important for good semiconductor
application area of developed methods. The prepara- properties. Using this approach, it was possible to
960 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
prepare a polymer combining semiconductor (charge The absence of side exchange reactions accounts
mobility of 3.5610 73 cm 2 V 71 s 71 ), electrolumines- for the extensive use of the Suzuki reaction in the
cence (luminance of up to 385 cd m 72 ) and photo- synthesis of so-called conjugated `small molecules' Ð
voltaic (solar cell efficiency of up to 0.77%) proper- oligomers having relatively low molecular mass. These
ties. It should be noted, however, that these values compounds have a number of advantages over poly-
are rather far from the current record characteristics. mers, for example, the possibility to prepare extra
The Suzuki reaction is widely used to prepare pure materials, which is especially important for
polymers with a narrow band gap to be used in organic electronics. Conjugated oligomers are used as
organic photovoltaic cells 695, 710 (polymers P1 ± P4, semiconductor materials in organic field effect tran-
Scheme 155). It was shown 707 that optimization of sistors, 713, 714 phosphorescent molecules in organic
the purification methods and techniques for solar cell light emitting diodes 715 and active layers in organic
fabrication based on these polymers substantially solar cells. 716 A comparison of two methods for
increases their operation efficiency. preparation of the oligomers, by the Suzuki reaction
Scheme 155 and by direct C7H-arylation, has been reported 717
R R (Scheme 156). With the use of organoboron com-
pounds, the yield of the target product was 1.5 times
X
higher than in the direct arylation reaction (60% and
O O + 40%, respectively).
B B The Suzuki reaction was used to synthesize star-
S S
O O shaped molecules with a triphenylamine moiety as a
F F branching unit and dicyanovinyl groups connected by
bithiophene p-conjugated spacers. The molecules dif-
Pd(PPh3)4 fered only by the length of the terminal aliphatic
+
Br Br
2M Na2CO3, DME groups, which was employed to study the effect of
S S these groups on photovoltaic properties. It was shown
R R that short alkyl substituents decrease the solubility
X but increase the operation efficiency of organic solar
cells; the best efficiency approached 5%. 697
S S
Scheme 156
R R S
N N
Suzuki
O O reaction
2 + B B R R S
Br O O N N
S S
S S
R R S
N N S S
direct arylation
2 +
Br Br R R
S S
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 961
pentadithiophene are used in the synthesis of conju- phene derivative under the Stille reaction condi-
gated polymers for organic photovoltaics and thin-film tions. 729 The polymer yield was 90%, the weight-
field effect transistors, as their organoboron analogues average molecular mass was 60 kDa and the polydis-
are unstable under the Suzuki reaction conditions, persity was 1.8. In a recent study, a similar trime-
which results in the formation of low-molecular-mass thyltin monomer was introduced in the Stille reaction
polymers. For example, Zhu et al. 726 used the Stille to produce a block copolymer based on poly(3-hex-
reaction to prepare a copolymer based on 4,4-bis(2- ylthiophene) and poly(diketopyrrolopyrroleterthio-
ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b 0 ]dithiophene and phene) blocks (Scheme 160). 730 The weight-average
2,1,3-benzothiadiazole with M n of up to 30 kDa and molecular mass of the polymer reached 133.5 kDa at
a relatively narrow molecular-mass distribution a polydispersity of 1.89.
(1.4 ± 1.6) (Scheme 159). BaÈ uerle and co-workers 731 applied the Stille reac-
Scheme 159 tion of the same monomer to prepare a number of
donor ± acceptor p-conjugated thiophene-containing
R R S oligomers with dicyanovinyl acceptor groups; these
N N
Pd(PPh3)4 oligomers were employed as effective donor materials
+ PhMe in organic photovoltaic cells (Scheme 161). It was also
Br Br demonstrated in the study that the yield of the
Me3Sn SnMe3
S S
reaction products varies from 82% to 99% and
R R S decreases if toluene or THF serves as the solvent.
N N This can be attributed to the insufficient solubility of
the intermediate monoaddition products in toluene
and THF due to which they precipitate and cannot
S S n be involved in the further transformations.
R = BunEtCHCH 2
Scheme 161
CN
Pd(PPh3)4
By adding one more difunctional monomer, 5,5 0 - +
NC Br Me3Sn SnMe3 DMF
dibromo-2,2 0 -bithiophene, into this reaction, a series S n
S n
of copolymers with a random distribution of struc-
tural blocks and a weight-average molecular mass of CN CN
up to 30 kDa was prepared. Somewhat later, the Stille
NC S CN
cross-coupling successfully served for copolymerization x
C10H21
C6H13
N O
Br Pd2(dba)3, P(o-Tol)3
S + S
H Br Me3Sn S SnMe3 + PhCl
S
S Br
n O N
H13C6
H21C10
C8H17
C8H17
C6H13
C10H21
S S N
H O
S S
H13C6 n S
O
N
H21C10 m
C8H17
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 963
and polymer samples with higher molecular mass can Scheme 166
be prepared. C6H13
For example, Choi et al. 738 succeeded in the Oct
preparation of polymers with a number-average Oct
molecular mass of 147 kDa by adjusting the optimal N Y
S
a or b
O O Y
conditions for polycondensation of 3,4-ethylenedioxy- + S
thiophene and substituted 2,7-dibromofluorene
(Scheme 165). Oct
Scheme 165 X S X
C6H13
H S H Oct Oct
Oct
Pd(OAc)2
+ Br Br ButCO2K, N
O O
O O DMA, MW
Oct Oct S S
S
S
Oct Oct n
O O
(a) Stille reaction; X = Br; Y = SnMe3; Pd2(dba)3, P(o-Tol)3, PhCl;
n
71% yield, Mn = 9000;
Oct = n-C8H17 (b) direct arylation; X = H; Y = Br; Pd(OAc)(o-Tol),
P(C6H4OMe)3, Cs2CO3, THF; 96% yield, Mn = 56 000
The reaction was assisted by microwave radiation,
the reaction time was 30 min and the product yield
reached 89%. Dimethylacetamide was used as the From the material presented, one can see how
solvent, potassium pivalate served as the base and important is the selection of a particular synthetic
the catalyst (palladium acetate) amount used was as chart for the yield of the p-conjugated oligomers and
low as 1 mol.%. The polymer obtained demonstrated especially for molecular-mass characteristics of
good film-forming properties, which is important for p-conugated polymers. Each of the considered organo-
the fabrication of organic thin-film electronic devices metallic synthesis reactions has its advantages and
by solution methods. shortcomings for the preparation of functional materi-
Some papers are devoted to the synthesis by direct als for organic electronics. A recent trend is a more
arylation of highly efficient polymers for organic extensive use of the direct C7H arylation reaction
photovoltaics, which have been prepared formerly by owing to its simpler synthetic chart: there is no need
the Stille reaction. 739 For example, polymers based on to prepare organoboron, -magnesium and -tin deriva-
thieno[3,4-c]pyrrole-4,6-dione, 740 dithienosilole and tives for the Suzuki, Kumada or Stille reactions,
dithienogermole,741 cyclopentadithiophene and benzo- respectively; the problem of stability of these deriva-
thiadiazole 742 and some other compounds have been tives during the reaction is eliminated and, hence, the
synthesized in the presence of the Herrmann ± Beller molecular mass of the resulting conjugated polymers
palladium catalyst under various conditions. In each increases. However, the development of the direct
case, the polymer molecular mass was higher than C7H arylation technique is slowed down by the
that of analogous polymers obtained by the Stille need to use fairly expensive ligands, which are, more-
reaction. The advantages of synthesis of conjugated over, not universal and should be often selected anew
polymers by direct C7H arylation over the Stille for each substrate. Therefore, currently, the classical
reaction were demonstrated most clearly by Leclerc Suzuki, Kumada and Stille cross-couplings are still
and co-workers, 740 who considered polycondensation more popular. The most important tasks for this line
of bithiophene and thienopyrroledione monomers by of research in the near future are to study the
both methods (Scheme 166). The imide group in the possibility of performing the Suzuki reaction in an
thienopyrroledione monomer acts simultaneously as aerobic atmosphere, which is barely used now to
both a directing and an activating group for the prepare conjugated oligomers and polymers, and to
C7H bonds. In the case of direct synthesis, the search for new promising catalysts and ligands for
yield of the polymer proved to be higher, the molec- extending the scope of applicability of direct C7H
ular mass was six times higher, and the amount of arylation in the synthesis of organic semiconductors
wastes was three times lower. and luminophores.
Researchers pin a lot of hope on the direct C7H
arylation, further development of which may not only XV. Supramolecular gels as a new class of smart
reduce the prime cost of organic semiconductors and
increase the environmental safety of the production
materials
but also provide new conjugated polymers with high The development of new technologies will result, in
molecular masses and unique properties. the nearest future, in a very broad use of so-called
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 965
smart materials Ð i.e., materials that respond to changes in manifested both in solutions (dilute and concentrated)
the environment and change their properties in response to and in the condensed state. As a definite degree of
the external stimuli. This stimuli may include temperature, polymerization has been attained, spontaneous assem-
pressure, pH, the presence or absence of chemicals, irradi- bly of supramolecular polymers into a specific phase
ation, magnetic or mechanical treatment. The ability to (film, layer, membrane, vesicle, micelle, gel, mesomor-
finely controlling substance properties by varying the phous phase or crystal) may take place. 768 In supra-
above-mentioned conditions provides researchers with a molecular polymers that are formed upon the
powerful tool for the design of functional materials of the reversible assembly of bifunctional monomers, the
future. Therefore, the search for systems that behave as degree of polymerization (the number of monomers
smart materials and ways to control them is a topical contained in the polymer Ð an important character-
problem of the modern fundamental and applied science. istics of a polymer) is determined by the strength of
One of the methods for the design of controllable interaction of the terminal groups. To attain substan-
materials is supramolecular approach. Supramolecular tial degrees of polymerization at relatively low con-
chemistry is a multidisciplinary field of science com- centrations, it is necessary to construct monomers
bining organic, inorganic and physical chemis- with binding sites that can ensure high association
try. 743, 744 A key problem solved by supramolecular constants (K a ). None of the intermolecular interac-
chemistry is the synthesis of intricate multicomponent tions taken separately complies with the criteria
structures with specified architecture and properties. imposed on interactions suitable for the formation of
The essence of the supramolecular approach is in the supramolecular polymers with a high degree of poly-
use of weak intermolecular interactions including merization. 769 Indeed, for a single hydrogen bond,
hydrogen bonds, ion ± ion, ion ± dipole, van der Waals which has the required directionality, the association
and hydrophobic interactions, p ± p stacking and constants do not exceed 100 litres mol71 . A drawback
charge transfer complexes to combine molecular com- of the Coulomb interactions between ionic groups is
ponents bearing binding sites necessary for assembly the lack of directionality; therefore, these bonds give
into a dynamic supramolecular system. The binding rise to insufficiently clearly shaped aggregates. Hydro-
site is a part of a molecule able to form intermolec- phobic effects are applicable only in polar media.
ular bonds between appropriate molecular compo-
nents. The main feature of intermolecular interactions XV.1.b. Coordination polymers
is low energy (as compared with covalent bonds in One type of intermolecular interactions widely used in
organic molecules), which accounts for reversibility of the supramolecular synthesis are coordination bonds,
the assembly of molecular components. Hence, there which form the basis for coordination polymers
is the possibility to control the equilibria by changing (CPs) Ð supramolecular polymers composed of
the reaction conditions; any of the above-mentioned repeating organic molecules (di- or polytopic ligands)
types of stimuli can be used either separately or in and metal ions. 770 ± 774
combination. According to the most up-to-date and general
An important class of smart materials is repre- definition, 764 coordination polymers are high-molecu-
sented by supramolecular gels Ð non-rigid soft mate- lar-mass compounds composed of repeating organic
rials able to change their physical and chemical molecules and metal ions connected by intermolecular
properties and even the phase state depending on interactions. Of these, the strongest type of interaction
external conditions and external stimulus applied. is coordination bonding between the donor sites of
This Section is devoted to conceptual issues of the organic molecule (L) and the metal ion (M). If a
synthesis and application of the new class of dynamic ligand molecule contains several donor sites arranged
supramolecular materials Ð supramolecular gels and in the divergent fashion (divergent binding sites), it
their metal-containing analogues. can bind several metal centres into one supramolecule.
More detailed information and specific applications Translation of these bound groups (L7M) along one,
of such systems can be found in reviews, 745 ± 756 two or three directions gives rise to CPs. One-dimen-
collected works 757 and monographs. 758, 759 sional chains (1D, linear, zigzag-like and helical), two-
dimensional networks (2D, non-interpenetrating and
XV.1. Supramolecular and coordination polymers interpenetrating networks) and three-dimensional
XV.1.a. Supramolecular polymers frameworks (3D, non-intersecting and interpenetrating
Supramolecular polymers are ordered polymeric struc- frameworks) can be formed in the crystal (Fig. 33).
tures consisting of monomeric units that are held The order of arrangement of CP components in
together by reversible and highly directional secondary three dimensions, the possibility of varying the nature
interactions. 760 ± 763 The latter comprise ion ± ion and and the size of tectons and dynamic properties of the
ion ± dipole interactions, coordination bonds, hydrogen frameworks impart unique properties to crystalline
bonds and cation ± p-system, p ± p-stacking, dipole ± di- coordination polymers. These compounds are being
pole, metallophilic and van der Waals interactions and actively studied as electric conducting materials; cata-
solvatophobic effects. 764, 765 Supramolecular interac- lysts for a variety of organic reactions including
tions that may combine molecular building blocks stereo- and enantioselective ones; materials with con-
(tectons) 766 in a programmed and reproducible man- trollable magnetic properties, in particular, materials
ner give rise to supramolecular synthons. 767 capable of cooperative spin-crossover; materials with
In the first stage of the reaction between comple- unusual optical and nonlinear optical properties; sen-
mentary tectons, the intermolecular association gives sors for metal ions and small molecules. 775 ± 784
rise to polymeric properties of the associates being
966 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
..
..
.. and co-workers. 805 The currently known applications
..
..
..
..
of SMMGs include catalysis 806 ± 810 and design of
luminescence, 811, 812 photochromic 813 and spin-cross-
over materials. 814, 815 Supramolecular gels are applied
to obtain films, 816 nanotubes 817 and nanowires, 818 to
M M M M M M
transport 819 and remove organic compounds from
1D chains M aqueous systems; 820 they serve as porous templates to
M grow inorganic materials, 821 as templates for organo-
M M M M polymerization; 822 gels based on G-quartet nucleic
M M M
acids are also known. 823, 824
M M M
Gels based on low-molecular-mass gelators
M M M (LMMGs) are usually prepared by heating the gelator
M M 3D frameworks
in the appropriate solvent followed by cooling the
2D networks resulting isotropic supersaturated solution to room
temperature. The gelation process competes with the
Figure 33. Schematic view of one-, two- and three-dimensional formation of crystals and amorphous precipitates. As
coordination polymers.775 regards the degree of molecular ordering, a gel can be
considered to be an intermediate state (most often,
metastable) between these phases. During the gelation,
the self-assembly of LMMG affords long polymeric
It is noteworthy that particular properties of third- fibrillar aggregates, which are then interwoven to give
generation porous frameworks (the ability to be rear- a three-dimensional template, which traps molecules of
ranged under the action of external factors, which the medium, most of all, due to surface tension. As a
include light, temperature or guest molecules) are result, the mobility of the solvent molecule is
analogous to the properties of materials based on restricted and the whole material acquires some fea-
molecular gels. 785 As noted above, crystalline coordi- tures of a solid.
nation polymers have been comprehensively studied A key characteristics of a supramolecular gel is the
with the goal of practical application (see, for exam- reversible gel ± sol transition, which occurs on heating
ple, Refs 775 and 777); however, non-crystalline sys- and distinguishes SMG from a polymeric gel. Owing
tems having similar structures, first of all, metallogels to this feature, these materials can be used as thermal
we are interested in have been rather little sensors: above a definite temperature (called gelation
studied. 750, 754 temperature, T gel ), the non-flowing gel converts to the
flowing sol. Apart from this feature called thermo-
XV.2. Supramolecular gels and metallogels tropy, SMGs can change upon replacement of the
The search for systems able to reversibly change the solvent (lyotropy) and upon mechanical treatment
structure and properties under the action of external (thixotropy).
factors (stimuli-responsive materials) is a topical prob- A supramolecular gel can respond to other types
lem of modern materials science and has a broad of external action (light or chemicals) if a light-
range of potential applications. 786 One of the ways sensitive or receptor moiety has been incorporated in
for producing materials with indicated properties may the LMMG molecule. The diverse opportunities
be the use of monomeric tectons that are self- opened up by incorporating chemically different moi-
assembled to a supramolecular polymer. The supra- eties with various physical properties into the LMMG
molecular assembly thus formed can change the struc- structure are implemented in the design of thermo-
ture and even be destroyed under a certain external chromic and conducting gels and oriented liquid-crys-
action but can be restored with full recovery of the talline physical gels (see Section XV.3).
initial properties after the action has been termi- At the current stage of development of chemistry,
nated. 787 This behaviour is based on reversibility of it is impossible to reliably predict the ability of some
formation of supramolecular bonds. organic compound to convert a particular solvent into
Examples of stimuli-responsive materials are supra- a gel considering only its molecular structure. Exam-
molecular gels (SMGs), which represent a type of ples of low-molecular-mass gelators are shown in
supramolecular polymers. Supramolecular gels are Fig. 34. Most of known LMMGs include urea, carbo-
able to change their structure (and, hence, properties) hydrate or amino acid moieties. This is related to the
under the action of an enormous number of external known properties of multiple hydrogen bonds typical
factors of different nature. Indeed, known SMGs can of these classes of compounds, in particular, the
be anion-sensitive, 788 thermally sensitive, 789 ± 791 metal- directionality and energy characteristics. Only a
sensitive, 792 CO 2 -sensitive, 793, 794 redox-sensitive, 795 ± 797 minor portion of LMMGs are prepared by modifica-
magnetically sensitive, 798 mechanically sensitive, 799 tion of known structures, while the other are discov-
sound-sensitive 800 and light-sensitive. 801 ± 804 Gel for- ered serendipitously. 752, 825
mation based on low-molecular-mass components is Gels based on LMMGs are often susceptible to
the dominant subject matter of research of many spontaneous micro- and macrodestruction or phase
research teams, first of all, in materials science. separation upon mechanical treatment or on ageing.
V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014) 967
HO OH
R1
OC16H33 O 7 OOC
HN COO7 CH3(CH2)n(CF2)mCF3
NH + +
OC16H33 O N N
H33C16 C16H33
R2
O O
O OCH2CO2
O
O
H H H
O O O O
OH N
HO H O H25C12 N H
N N O N
H O +
O N C16H33
H25C12 N
O H N
H O H N H
N N O
H O H
O O
O O
R (CH2)n R
N N N N
H H H H
O
O(CH2)2C8F17
R = C12H25,
O(CH2)2C8F17
To prevent these undesirable processes, the structure ticipate (at least, formally) in the gel formation. The
of the formed gel could be secured by intermolecular second approach is based on the participation of the
covalent bonds in side chains (e.g., by polymerization metal in the proper gelation process via coordination
involving a double bond or a triple bond; reaction of bonding with the donor sites of the exodentate ligand
the hydroxy groups with the diisocyanate linker) 751 or molecules. In this case, the metallopolymer and the
by adding a reinforcing polymer such as cellulose. 826 whole SMMG can be classified as a coordination
While developing new, low-molecular-mass gela- polymer. The third approach is based on introduction
tors, one should consider the following key factors: of a metal-containing component into the structure of
(i) the presence of sites for rather strong self-comple- the SMG prepared beforehand. All three approaches
mentary and unidirectional intermolecular interactions are schematically shown in Fig. 35.
for one-dimensional self-assembly; (ii) the possibility Examples of using the first approach have been
of lateral interchain interaction with lower energy reported in two publications.806, 827 DoÈ tz and co-work-
than the main interaction along the chain; (iii) the ers 806 prepared the Fischer type cobalt carbene com-
possibility of controlling the nanofibre ± solvent inter- plex, which contained groups capable of gel
facial energy in order to regulate the solubility and formation, namely, a sugar residue and a hydrophobic
prevent crystallization; (iv) the existence of ways of alkyl tail. The resulting complex was able to gelate
affecting the degree of branching during the formation
of a 3D network.
UV
10 mm
UV
Figure 38. Samples of silica aerogels prepared by supercritical
drying.836
N N
CF3SOÿ
3
H2N N NH2
500 nm 900 nm
XVI. Conclusion
Hole mobility /cm2 V71 s71
One of the objectives of this review was to dem- Among the currently developed approaches to
onstrate the listed advantages by examples of partic- increasing the selectivity of heterogeneous catalysts,
ular catalytic reactions of organic synthesis the range most of which are discussed in this review, the
of which is being constantly extended. One more following approaches appear to be most promising
problem faced by catalysis in organic synthesis is (i) development of methods for grafting noble and
practical implementation of enantioselective methods transition metal complexes on solid porous matrices
for the preparation of organic compounds, which is a of various nature in order to increase their stability;
very large and highly promising area. Obviously, (ii) study of the size effects in selective organic reac-
catalytic methods will predominate along this line tions catalyzed by supported monometallic catalysts in
including both classical methods (involving transition order to determine the size of supported metal par-
metals) and organocatalysis. ticles that ensures the highest level of selectivity and
However, despite the enormous scientific and prac- development of methods for the preparation of cata-
tical interest in catalytic transformations of organic lysts with a narrow (in the ideal case, monodisperse)
molecules, the industrial use of these processes is still particle size distribution; (iii) study of the effect of the
not very extensive. One reason is that most of the nature of the support (metal ± support interaction) and
discovered catalytic reactions of organic synthesis are the second metal (synergistic effects) for fine tuning of
homogeneous, i.e., they involve soluble organic com- the electronic state of the active metal in order to
plexes of transition (including noble) metals as cata- minimize the side reactions.
lysts. The advantages provided by these processes Despite the necessity to carry out huge research
(high selectivity to target products, which often along this line, it is possible even now to cite quite a
reaches 100%, in particular in the synthesis of definite number of examples of heterogeneously catalyzed
stereoisomers and enantiomers) are difficult to imple- organic reactions implemented in practice. This con-
ment in industry due to the problems of catalyst clusion is supported by the review chapter devoted to
separation from other reaction components (reactants, analysis of the recently commissioned industrial proc-
products and solvents). esses of organic synthesis on heterogeneous catalysts.
Therefore, a highly important direction in this The final part of the review outlines one more
research area is to develop approaches to catalytic modern trend of the development of organic chemis-
reactions of organic synthesis in the presence of try, which finds more and more extensive practical
heterogeneous catalysts in which metal complexes or application: the use organic reactions for the synthesis
even metal nanoparticles supported on various solid of functional materials, including the materials that
materials serve as the active components. Transition change properties in response to external influence.
to heterogeneous catalysts provides additional advan- Thus, the challenges of the modern society and the
tages, including effective separation of the catalyst increasing demands of high-technology-based sectors
from the reaction medium for repeated use; a wider of modern industry stipulated a new phase in the
range of applicable solvents because in this case, the development of organic synthesis. The increase in the
problem of solubility of metal complexes, which serve efficiency of catalytic processes, especially the selectiv-
as catalysts in homogeneous reactions, is eliminated; ity of heterogeneous catalytic systems and stability/
implementation of cascade or one-pot processes owing regeneration of homogeneous catalytic systems, is the
to the design of sites having various functionality on key trend of the development of catalytic technologies
the surface of a heterogeneous catalyst (bimetallic in the near future.
catalysts, support modification and the like). The review was prepared with the financial support
The second half of the review devoted to charac- of the Russian Foundation for Basic Research
teristic features of reactions of organic synthesis on (RFBR), Council at President of the Russian Feder-
heterogeneous catalysts indicates that the above-listed ation, Presidium of the RAS and the Skolkovo Foun-
advantages of heterogeneous catalytic processes cannot dation: V P Ananikov and co-workers (Section V) Ð
be embodied unless high selectivity to the target RFBR Project Nos 13-03-01210, 13-03-12231 and 14-
reaction products is achieved. Solution of this prob- 03-31465; V I Bukhtiyarov and co-workers (Sec-
lem lies in the molecular design of the optimal tion IX) Ð RFBR Project No. 13-03-01003, Grants of
catalyst. This procedure should be based on the the Council at President of the Russian Federation
knowledge gained from detailed investigation of the NSh-5340.2014.3, Presidium of the RAS 24.51 and
mechanisms of catalytic reactions and structure of Skolkovo Foundation (Agreement of Provision of a
active sites, in particular, using model catalysts. Grant to Russian Educational Institution of Novem-
Therefore, a highly important modern trend is devel- ber 28, 2013, No. 1); S Z Vatsadze and co-workers
opment of new physical methods for investigation of (Section XV) Ð RFBR Project No. 14-03-91160
heterogeneous catalysts including methods that are GFEN-a; A D Dilman and co-workers (Section II) Ð
suitable for in situ studying the state of the surface, RFBR Project Nos 13-03-12074, 14-03-00293 and
i.e., during the catalytic process. Elucidation of the MD-4750.2013.3; I V Koptyug and co-workers (Sec-
relationship between the properties of the catalyst tion XIII) Ð RFBR Project Nos 14-03-00374-a, 14-03-
surface and the activity and selectivity of transforma- 31239-mol-a, 12-03-00403-a, 14-03-93183-MSKh-a and
tion of organic compounds in particular reactions Grants of the Council at President of the Russian
would allow for the manufacture of catalysts of Federation MK-4391.2013.3 and MK-1329.2014.3;
optimal composition for low-waste and waste-free V A Likholobov and co-workers (Section XI) Ð
processes of organic synthesis to prepare compounds RFBR Project No. 13-03-12258; V G Nenaidenko and
of various classes. co-workers (Section VII) Ð RFBR Project Nos 14-03-
972 V P Ananikov et al. Russ. Chem. Rev. 83 (10) 885 ± 985 (2014)
31119 mol_a and 13-03-90413 Ukr_f_a; M S Nechaev 31. D O'Hagan J. Fluorine Chem. 131 1071 (2010)
and co-workers (Section VI) Ð RFBR Project No. 13- 32. J Wang, M SaÂnchez-RoselloÂ, J L AcenÄa, C del Pozo,
03-12240; S N Osipov and co-workers (Section III) Ð A E Sorochinsky, S Fustero, V A Soloshonok, H Liu
RFBR Project Nos 12-03-00557 and 12-03-93111; S A Chem. Rev. 114 2432 (2014)
Ponomarenko and co-workers (Section XIV) Ð RFBR 33. E V Nosova, G N Lipunova, V N Charushin,
Project Nos 13-03-01315 and 13-03-12451; A A Rempel O N Chupakhin Ftorsoderzhashchie Aziny i Benzaziny
and co-workers (Section VIII) Ð RFBR Project (Fluorine-Containing Azines and Benzazines)
Nos 14-03-00869; A Y Stakheev and co-workers (Sec- (Ekaterinburg: Ural Branch of the Russian Academy of
tion X) Ð RFBR Project Nos 13-03-12176 ofi_m and Sciences, 2011)
12-03-31487-mol_a; S V Sysolyatin and co-workers 34. V N Charushin, E V Nosova, G N Lipunova,
(Section XII) Ð RFBR Project Nos 13-03-12193 and O N Chupakhin Ftorkhinolony: Sintez i Primenenie
13-03-12178; and A O Terent'ev and co-workers (Sec- (Fluoroquinolones. Synthesis and Application) (Moscow:
tion IV) Ð RFBR Project Nos 13-03-12074 and 14-03- Fizmatlit, 2014)
00237. 35. K MuÈller, C Faeh, F Diederich Science 317 1881 (2007)
36. M E Phelps Proc. Natl. Acad. Sci. USA 97 9226 (2000)
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