Huguet Et Al-2014-Chemistry - A European Journal-QUESTO PDF
Huguet Et Al-2014-Chemistry - A European Journal-QUESTO PDF
Huguet Et Al-2014-Chemistry - A European Journal-QUESTO PDF
201405528 Communication
Abstract: The nickel-catalyzed direct carboxylation of al- The hydrocarboxylation of activated unsaturated hydrocar-
kenes with the cheap and abundantly available C1 build- bons with CO2[3] is an established methodology in organic
ing block carbon dioxide (CO2) in the presence of a base chemistry to yield either a,b- (for alkynes),[4] b,g-unsaturated a-
has been achieved. The one-pot reaction allows for the branched (for allenes and 1,3 alkadienes),[5] or a-branched car-
direct and selective synthesis of a wide range of a,b-unsa- boxylic acid derivatives (for styrenes),[6] but requires the stoi-
turated carboxylates (TON > 100, TOF up to 6 h 1, TON = chiometric use of reductants (i.e., AlEt3, hydrosilanes, Et2Zn,
turnover number, TOF = turnover frequency). Thus, it is RMgX) or directing groups in the substrate.[6c]
possible, in one step, to synthesize sodium acrylate from The catalytic carboxylation of unsaturated hydrocarbons
ethylene, CO2, and a sodium salt. Acrylates are industrially with CO2 to a,b-unsaturated carboxylates (i.e., acrylates) has
important products, the synthesis of which has hitherto been difficult for three decades, although, in the 1980s,
required multiple steps. Hoberg et al.[7] reported the nickel-catalyzed reaction of al-
kenes and isocyanates (isoelectronic to CO2) to acrylamides.
Since the early results of Hoberg et al., the cleavage of inter-
mediately formed metallalactones, in particular nickelalac-
The exploitation of carbon dioxide (CO2) for the production of tones,[8] has been a challenging route for such catalytic reac-
globally used chemicals such as formic acid,[1] is of huge indus- tions: for stereoelectronic reasons, five-membered “Hoberg
trial interest, because CO2 is a cheap and abundantly available complexes” do not readily undergo b-H elimination and their
C1 building block.[2] Nevertheless, only a few reactions and cat- cleavage with auxiliaries such as electrophiles (i.e., alkyl hal-
alysts enable the straightforward catalytic functionalization of, ides[9] or protons[9g, 10]), Lewis acids,[9g, 10, 11] a combination of
for example, alkenes with CO2 to industrially relevant target both,[12] thermally,[9c, 10, 13] or even sonochemically,[10] has not led
molecules such as acrylates. Acrylates and their downstream to catalysis. The cleavage of nickelalactones with sterically hin-
products are ubiquitous in daily life as hygiene products, coat- dered phosphazene bases is slow[11c] and, due to the mutual in-
ings, adhesives, and food preservatives and are globally manu- compatibility of strong bases, Lewis acids, and CO2, catalysis re-
factured on a multimillion ton level. mained a challenge. The same applies for other metals from
groups 4 (Zr),[14] 6 (Mo),[15] 8 (Fe, Ru),[16] 9 (Rh),[17] and 10 (Pd,
Pt).[18]
[a] Dr. N. Huguet, Dr. I. Jevtovikj, Dr. A. Gordillo, Dr. M. L. Lejkowski, Only recently have we been able to disclose the first two-
Dr. R. Lindner, Dr. M. Bru, Dr. A. Y. Khalimon, Prof. Dr. P. Hofmann, step catalytic synthesis of sodium acrylate from ethylene and
Dr. M. Limbach CO2 based on a nickel catalyst (TON 10),[19] as a) we targeted
CaRLa (Catalysis Research Laboratory)
Im Neuenheimer Feld 584, 69120 Heidelberg (Germany) the exergonic reaction to an acrylic acid salt instead of the
Fax: (+ 49) 621-60-6648957 highly endergonic formation of acrylic acid (DG = 21 vs.
E-mail: [email protected] 59 kJ mol 1[20] in THF) and b) overcame the kinetically unfeasi-
[b] Dr. F. Rominger, Prof. Dr. P. Hofmann ble b-H elimination from the dtbpe-ligated nickelalactone
Ruprecht-Karls-Universitt Heidelberg
1 (DG° = 103 kJ mol 1)[19] by its a-deprotonation with an alkox-
Organisch-Chemisches Institut
Im Neuenheimer Feld 270, 69120 Heidelberg (Germany) ide base. In this communication we will address the develop-
[c] Dr. S. A. Schunk ment of an efficient one-pot catalyst system, which has previ-
hte GmbH ously been hampered by being limited to a small set of ligands
Kurpfalzring 104, 69123 Heidelberg (Germany) and substrates, and by the need to separate lactone formation
[d] Dr. M. Limbach and its cleavage due to the lack of a base capable of tolerating
BASF SE
CO2.
Synthesis and Homogeneous Catalysis
Carl-Bosch-Strasse 38, 67056 Ludwigshafen (Germany) The reaction of 1 with sodium 2-fluorophenoxide (2 equiv)
Supporting information for this article is available on the WWW under led to quantitative decarboxylation to ethylene complex 2 by
31
http://dx.doi.org/10.1002/chem.201405528. P NMR, whereas acrylate p-complex 3 was formed in a clean
Chem. Eur. J. 2014, 20, 16858 – 16862 16858 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication
1[a] 3 80 50
Table 1. Variation of ligand and solvent.
2[a] 4 80 50
13[a] 1 80 50
tate phosphines (i.e., PPh3, PtBu3) and small bite-angle ligands
(i.e., dtbpm, dppm) failed in the reaction. Comparably high
TONs (10–16) were obtained with the electron-rich P-stereo- [a] Ligand (0.22 mmol), Ni(COD)2 (0.2 mmol), CO2 (10 bar), C2H4 (5 bar),
sodium phenoxide (10 mmol); [b] As [a] but ligand (0.11 mmol), Ni(COD)2
genic bisphosphine ligands (S)-BINAPINE,[23] (S,S’,R,R’)-Tang- (0.1 mmol), 100 8C. [c] As [b] with zinc (10 mmol), CO2 (20 bar), C2H4
Phos,[24] (1R,1’R,2S,2’S)-DuanPhos,[25] and (R,R)-BenzP*,[26] where- (10 bar).
as dcpf, HiersoPHOS-1,[27] (R,R)-QuinoxP*[28] and the bisphos-
pholane (R,R)-Me-DuPhos were only moderately active (Table 1,
TON 1–4).[11b] In the homologous series of bidentate ligands
dippe, dippp, and dippb, a C2–3 bridge between the donor as its derivatives bearing substituents with + I effect in ortho-
atoms turned out to be beneficial (TON up to 6), whereas position (i.e., sodium 2-methyl- and 2,6-dimethyl-phenoxide,
amongst the substituents at the P-donor a tBu or iPr group Table 2, entries 2 and 3) gave comparably low TONs (ca. 4). In
gave the highest activity (TONs of 9 and 6, respectively). a series of fluoro phenoxides (substituent with I effect), the
The solvent had a major impact on the reaction outcome meta- or even better ortho-substituted derivative led to an in-
(Table 1), whereas ligands such as BenzP* were only moderate- crease in TON but not the para-substituted one (TON 8, 10,
ly active in DMF (or inactive in MeOH), apolar and aprotic sol- and 2, respectively, cf. Table 2, entries 3, 4, and 12). This trend
vents like ethers (THF, dioxane) or even toluene led to higher holds true for DuanPhos (TON 16 and 21, respectively, cf.
reactivity (TON 17). In chlorobenzene oxidative addition to Table 2, entries 4 and 5), albeit at a lower level. The activity of
form NiII turned out to be a limiting side-reaction.[29] Even the phenoxide seems to correlate with its pKa value in H2O
Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16859 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication
Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16860 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication
Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16861 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Communication
Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16862 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim