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International Edition: DOI: 10.1002/anie.201910304

Carboboration Hot Paper German Edition: DOI: 10.1002/ange.201910304

Palladium(0)-Catalyzed Directed syn-1,2-Carboboration and

-Silylation: Alkene Scope, Applications in Dearomatization, and
Stereocontrol by a Chiral Auxiliary**
Zhen Liu, Jiahao Chen, Hou-Xiang Lu, Xiaohan Li, Yang Gao, John R. Coombs,
Matthew J. Goldfogel, and Keary M. Engle*

Abstract: We report the development of palladium(0)-cata-

lyzed syn-selective 1,2-carboboration and -silylation reactions
of alkenes containing cleavable directing groups. With B2pin2
or PhMe2Si-Bpin as nucleophiles and aryl/alkenyl triflates as
electrophiles, a broad range of mono-, di-, tri- and tetrasub-
stituted alkenes are compatible in these transformations. We
further describe a directed dearomative 1,2-carboboration of
electron-rich heteroarenes by employing this approach.
Through use of a removable chiral directing group, we
demonstrate the viability of achieving stereoinduction in
Heck-type alkene 1,2-difunctionalization. This work introdu-
ces new avenues to access highly functionalized boronates and
silanes with precise regio- and stereocontrol.

Introduction

Metal-catalyzed 1,2-carboboration of alkenes is a powerful

means of simultaneously forming a C(sp3)@C and a C(sp3)@B
bond in a single step with multiple levels of selectivity
control.[1] Indeed, successful examples of catalytic 1,2-carbo- Scheme 1. Background and project synopsis.
boration have been developed with copper,[2] palladium,[3]
nickel,[4] and dual catalyst systems.[5] Of the various coupling
partners that can be engaged in 1,2-carboboration, organo- capable of functionalizing mono-, di- and tri- substituted non-
halides and pseudohalides are particularly important, given conjugated alkenes[4a,b] without formation of competitive
the structural diversity and widespread availability of these chain-walking products.[6, 7] These reactions are believed to
electrophiles (Scheme 1 A). In this area, classical limitations proceed via a NiI-Bpin intermediate, which generally delivers
have included the scope of compatible alkenes and associated the Bpin group to the less substituted carbon atom. With
issues with regiocontrol; indeed, the vast majority of success- trisubstituted alkenes, the reactions are highly regioselective,
ful examples involve activated alkenes, such as styr- whereas with non-symmetric 1,2-disubstituted alkenes and
enes[2a,f, 3a, 4c,d, 5] or norbornenes (Scheme 1 B).[2d, 3b] Previously, terminal alkenes, regiomeric ratios (r.r.) are variable and
Xiao and Fu developed a Cu-catalyzed regiodivergent 1,2- controlled by a combination of steric and electronic factors.
alkylboration of non-conjugated terminal alkenes containing To complement these approaches, we reasoned that
a proximal heteroatom.[2c] Recently, Brown has developed an a substrate-directed strategy involving palladium catalysis
elegant series of nickel-catalyzed 1,2-arylboration methods could enhance reactivity with hindered substrates (e.g.,
tetrasubstituted alkenes[8]) and provide a means of controlling
regioselectivity in a manner that is independent of the alkene
[*] Dr. Z. Liu, J. Chen, H.-X. Lu, X. Li, Dr. Y. Gao, Prof. K. M. Engle substitution pattern. Previously, our lab[9] and others[10] have
Department of Chemistry, The Scripps Research Institute developed a toolkit of hydro- and difunctionalization reac-
10550 North Torrey Pines Road, La Jolla, California 92037 (USA)
tions of alkenyl carbonyl compounds bearing the 8-amino-
E-mail: [email protected]
quinoline[11] (AQ) directing group. As part of this effort, we
Dr. J. R. Coombs, Dr. M. J. Goldfogel
described an anti-selective 1,2-carboboration of alkenyl
Chemical Development, Bristol-Myers Squibb
One Squibb Drive, New Brunswick, New Jersey 08903 (USA) carbonyl compounds that initiates via Wacker-type carbopal-
[**] A previous version of this manuscript has been deposited on ladation (Scheme 1 C).[3c–e] Though useful in its own right, this
a preprint server (https://doi.org/10.26434/chemrxiv.8865143.v2). method is limited in terms of the carbogenic groups that can
Supporting information and the ORCID identification number(s) for be introduced (indole-type nucleophiles) and the alkene
the author(s) of this article can be found under https://doi.org/10. scope (terminal and 1,2-disubstituted alkenes). We hypothe-
1002/anie.201910304. sized that these issues could be overcome by developing

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a catalytic system that instead initiates via Heck-type 1,2- carbonyl compounds, which react via five-membered pallada-
migratory insertion.[9d,f, 10b,e] Based on this idea, herein we cycles, the reaction was largely insensitive to the alkene
describe a Heck-type directed 1,2-carboboration that pro- substitution pattern. Di-, tri-, and even tetrasubstituted
ceeds via a Pd0/PdII redox manifold (Scheme 1 D). In addition alkenes were all competent, leading to a variety of secondary
to tolerating essentially all possible alkene substitution and tertiary alkyl boronates in excellent yields (4 a–k). These
patterns, the protocol can also be applied in directed results stand in contrast to our previously developed directed
dearomative 1,2-carboboration of electron-rich heterocycles. 1,2-difunctionalization reactions involving Wacker-type nu-
The generality of this directed 1,2-difunctionalization ap- cleopalladation,[3c, 9b,c,e] which are highly sensitive to steric
proach via Pd0/PdII catalysis is demonstrated through the hindrance and are incompatible with tri- and tetrasubstituted
realization of a 1,2-carbosilylation method by using PhMe2Si- alkenes. Substrate 1 h, which is derived from Vince lactam,[14]
Bpin[12] in place of B2Pin2. Lastly, stereoinduction by use of underwent arylboration smoothly to give product 4 h, which
a chiral directing group is shown. bears four substituents on the same face of the cyclopentane
ring. Furthermore, from tetrasubstituted alkene 1 k, the
resulting product contains two contiguous quaternary centers,
Results and Discussion a motif that is inaccessible using existing arylboration
methods.
To initiate our study, we first selected 8-aminoquinoline The reaction also works reasonably well for substrates
(AQ)-masked 3-butenoic acid (1 a) and (E)-3-hexenoic acid containing one additional methylene spacer between the C=C
(1 c) as our pilot alkene substrates, phenyl triflate (2 a) as the bond and the carbonyl groups (4 l–p), which react via six-
electrophile, and B2pin2 (3 a) as the boron-based nucleophile. membered palladacycles. However, with these substrates, the
We elected to use a catalyst system consisting of Pd2dba3 and reaction is more sensitive to steric hindrance. With 1,2-
a phosphine ligand.[10b] We hypothesized that the phosphine disubstituted alkene 1 m, the product (4 m) was obtained in
ligand would coordinate to Pd0 and promote oxidative 85 % yield, which is slightly diminished compared to analo-
addition to the aryl triflate. After extensive screening of gous earlier examples (4 b–4 d). With trisubstituted alkene 1 r,
different ligands, bases, and reaction solvents (see the no reaction was observed. We attribute this pattern of
Supporting Information (SI) for details), we identified an attenuated reactivity to less favorable kinetics and thermo-
optimal combination: i-Pr2NEt as base and t-AmylOH as dynamics for 1,2-migratory insertion to form a six-membered
solvent with a Buchwald-type ligand,[13] such as RuPhos, palladacycle versus a five-membered palladacycle. Substrates
XPhos, or Cy-JohnPhos (L). Under these conditions syn-1,2- with even more distal alkenes, including terminal alkene 1 s,
arylborylated products 4 a and 4 c could be isolated in nearly were unreactive under the standard conditions. Interestingly,
quantitative yield without observable formation of regio- and an alkenyl amine substrate containing a picolinamide (PA)
stereoisomers based on 1H NMR. directing group also underwent 1,2-arylboration in moderate
We then tested the alkene scope of this Pd0-catalyzed 1,2- yield (4 q). Importantly, across all of these examples, the
arylboration (Table 1). Pleasingly, we found that a remarkably phenyl group was reliably delivered to position distal to the
broad collection of alkenes were reactive. For b,g-unsaturated directing group, and the Bpin group moiety was installed

Table 1: Alkene scope of 1,2-arylboration.[a]

[a] Reaction conditions: 1 a–q (0.05 mmol or 0.1 mmol), 2 a (1.5 equiv), 3 a (2 equiv), Pd2dba3 (3 mol %), L (6 mol %), i-Pr2NEt (2 equiv), 4 b MS (15–
30 mg), 90 8C, N2, 38–44 h. Percentages refer to isolated yields. Unless otherwise noted, diastereomeric ratio (dr) was found to be > 30:1 in all cases.
[b] 2 a (3 equiv), 3 a (3 equiv), Pd2dba3 (5 mol %), L (10 mol %), i-Pr2NEt (3 equiv), 100 8C. [c] 2 a (2 equiv), 3 a (3 equiv), Pd2dba3 (4.5 mol %), L
(9 mol %), i-Pr2NEt (3 equiv). [d] The final product was oxidized to the corresponding alcohol with NaBO3·4 H2O (5 equiv) for ease of isolation.

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Table 2: Electrophile scope.[a] a class of inexpensive aryl electrophiles that are used on
industrial scale, making them attractive yet underutilized
coupling partners in alkene functionalization. To our delight,
phenyl fluorosulfate (2 j) was found to be a highly effective
electrophile in this 1,2-arylboration reaction, providing nearly
quantitative yield of 4 c (Scheme 3).

Scheme 3. Arylboration using phenyl fluorosulfate as the electrophile.

Given the broad scope of this reaction and its insensitivity

to alkene substitution patterns, we next questioned whether it
was possible to carry out directed dearomative 1,2-difunc-
[a] Unless otherwise specified, reaction conditions were as in Table 1. dr tionalization[16] of heteroarenes (Table 3). The three-compo-
values were found to be > 30:1 in all cases. [b] 2 d (2 equiv), 3 a (3 equiv).
[c] The final product was oxidized to the corresponding alcohol with
NaBO3·4 H2O (5 equiv) for ease of isolation. Table 3: Dearomative aryl/alkenylboration of heterocycles.[a]

proximal to the directing group, irrespective of alkene

substitution pattern, illustrating a unique aspect of this
directed 1,2-carboboration compared to other approaches.[1–5]
Next, we investigated the compatibility of carbon electro-
philes in this transformation (Table 2). An array of aryl
triflates containing substituents with different electronic
properties on the para or meta positions reacted smoothly
under the optimal conditions, delivering the corresponding
products, 4 r–4 u, in excellent yields. Notably, heteroaryl
triflates containing a Lewis basic N(sp2) atom (4 v and 4 w),
which are incompatible in many Pd-catalyzed alkene func-
tionalizations, are tolerated in this reaction, though slightly
lower yields were obtained. Gratifyingly, when we used
alkenyl triflates 2 h and 2 i as carbon electrophiles, 1,2-
alkenylboration could be achieved. Both 3-butenoic acid
and 4-pentenoic acid derivatives underwent alkenylboration
in good to excellent yields (4 x–4 z).
In order to demonstrate the methodQs operational sim-
plicity and practicality, we scaled up the alkene arylboration
[a] Reaction conditions: 1 t–v (0.05 or 0.1 mmol), 2 a–c, or 2 i (3 equiv),
reaction using 1 c as a model substrate (Scheme 2). Under
3 a (3 equiv), Pd2dba3 (5 mol %), L (10 mol %), i-Pr2NEt (3 equiv), 4 b MS
standard conditions, boronate 4 c was isolated in 91 % yield (20–30 mg), 100 8C, N2, 38–44 h. Percentages refer to isolated yields. The
(1.2 g). diastereomeric ratio (dr) was found to be > 30:1 in all cases. [b] Reaction
time of 96 h. [c] 1 v (0.1 mmol), 2 c (2 equiv), Pd2dba3 (4.5 mol %), L
(9 mol %).

nent 1,2-carboboration of heteroarenes would represent

a powerful way to prepare highly functionalized heterocycles.
Scheme 2. Gram-scale 1,2-arylboration. However, this type of reaction has not been previously
reported in the literature to the best of our knowledge. The
envisioned transformation is challenging for several reasons,
Considering the relatively expensive nature of aryl including the potential for competitive two-component
triflates, we also investigated other aryl electrophiles as Miyaura borylation, the relatively large energy barrier
triflate surrogates. Aryl fluorosulfates,[15] which can be readily associated with breaking aromaticity, and the possibility of
prepared from phenols and sulfurylfluoride (SO2F2), are undergoing rearomatization. Taking inspiration from an

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elegant recent report by Jia, Lautens and co-workers on Pd0- (6 a–6 i). 4-Pentenoic acid derivatives (such as 1 l), however,
catalyzed intramolecular dearomative arylboration of in- were incompatible in this transformation. In this case, only
doles,[17] we reasoned that the aforementioned issues could be a small amount of arylsilylated product was generated,
overcome through AQ-directed Heck-type migratory inser- together with alkene arylboration and hydroarylation by-
tion. products.
Gratifyingly, using this substrate directivity strategy, we To illustrate the synthetic utility of the 1,2-carboboration
were able to effect 1,2-carboboration of indoles and benzo- reaction, we performed a series of transformations on
furans in good yields and with excellent diastereoselectivity representative 1,2-carboborated products (Scheme 4). First,
(5 a–5 f). Several benzo-fused heterocyclic products contain-
ing a tertiary boronate group could thus be prepared in
a succinct manner. This dearomative transformation is not
without its limitations. Aryl triflates bearing strong electron-
withdrawing groups are incompatible in this reaction. With
indole substrates bearing a 2-substituent (1 w) or one extra
methylene spacer (1 x), similarly no reaction was observed. A
benzothiophene derivative 1 y was also unreactive in this
transformation.
To demonstrate the versatility of directed Heck-type 1,2-
difunctionalization chemistry, we next sought to develop
a method for three-component alkene 1,2-carbosilyation,
a transformation that would be synthetically enabling yet
remains underdeveloped in the literature.[18, 19] To this end, we
tested SuginomeQs PhMe2Si-Bpin reagent[12] (3 b) in place of
B2pin2 (3 a). Gratifyingly, after brief optimization we identi-
fied conditions for alkene 1,2-carbosilylation (Table 4).[20]

Scheme 4. Diversification of arylborylated products.

Table 4: Scope of alkene aryl/alkenylsilylation.[a]

we carried out a 2-step transamination sequence to remove

the AQ directing group, following VerhoQs procedure.[21]
Compounds 4 c, 4 j, and 4 l were successfully transformed to
the corresponding pyrrolidine amides in excellent yields. In
addition, with Ni(tmhd)2 as a mediator, methanolysis of 4 c
was achieved in 78 % yield.[22] Finally, the boronate group of
8 c was transformed to a vinyl and fluoro group (10 and 11,
respectively) using literature methods.[23, 24]
To conclude this study, we aimed to demonstrate the
viability of establishing the absolute configuration of the
newly installed stereocenters through use of a chiral bidentate
directing group to facilitate the migratory insertion step.[25, 26]
After some experimentation, we eventually identified 1-
(pyridin-2-yl)ethan-1-amine (as shown in substrates 1 za–1 zc,
Table 5),[27] which is commercially available in enantiopure
form, as a suitable chiral directing group. Under modified
conditions using increased catalyst and ligand loading, 1,2-
arylboration proceeded smoothly with terminal alkene sub-
[a] Reaction conditions: 1 a, 1 c, 1 z (0.1 mmol), 2 a–d, 2 g, 2 i (1.5 equiv), strate 1 za, forming product 7 a in good yield with 9:1 dr and
3 b (3 equiv), Pd2dba3 (5 mol %), L (10 mol %), i-Pr2NEt (2 equiv), 4 b MS no epimerization of the chiral auxiliary. With internal alkene
(30 mg), 100 8C, N2, 38–44 h. Percentages refer to isolated yields. substrates 1 zb and 1 zc, this strategy could be used to establish
two contiguous stereogenic centers (7 b and 7 c). While both
reactions provided similar diastereoselectivity to the terminal
Although silyl group transfer to the PdII center was generally case, the yields were diminished (51 % and 32 % for the Z-
favored over boryl group transfer, small amounts of the 1,2- and E- alkene isomers, respectively) with unreacted starting
carboborylated byproduct could nevertheless be detected. material detected in both cases, reflecting the sensitivity of the
This competitive pathway accounts for the slightly lower reaction to steric hindrance. Based on an X-ray crystal
product yields in this transformation. Representative exam- structure of the racemic form of product 7 a, we were able to
ples of alkene substrates and electrophiles were examined, assign the relative stereochemistry of the major diastereomer
and yields were consistently in the moderate to good range and hence establish the absolute configuration of the newly

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Table 5: Diastereoselective arylboration using a removable chiral di- (50.8 mg, 0.2 mmol), Pd2(dba)3 (2.8 mg, 3 mol %), Cy-JohnPhos
recting group.[a] (2.2 mg, 6 mol %), and 4 c molecular sieves ( & 28 mg). The vial
was sealed with a screw-top septum cap and was then evacuated and
backfilled with N2 (X 3). Under positive N2 pressure, aryl or alkenyl
triflate (0.15 mmol), i-Pr2NEt (34.8 mL, 0.2 mmol), and t-AmylOH
(0.2 mL) were added. All needle inlets/outlets were removed, and the
reaction was placed in a heating block that was pre-heated to 90 8C.
After 40–44 h, the black reaction mixture was allowed to cool to room
temperature and filtered through a short plug of celite. Upon
purification by column chromatography with 5:1 to 3:1 hexanes:E-
tOAc as the eluent, the pure product was obtained.

Acknowledgements

This work was financially supported by Scripps Research,

Bristol-Myers Squibb (Unrestricted Grant), and the National
[a] Reaction conditions: 1 za–zc (0.05 mmol), 2 a (1.5 equiv), 3 a Institutes of Health (5R35GM125052-02). Additionally, we
(2 equiv), Pd2dba3 (10 mol %), L (20 mol %), i-Pr2NEt (2 equiv), 4 b MS gratefully acknowledge Bristol-Myers Squibb for a Graduate
(20 mg), 100 8C, N2, 44–48 h. The final products were oxidized to the Fellowship (Z.L.), Tsinghua University Department of
corresponding alcohol with NaBO3·4 H2O (5 equiv) for ease of isolation.
Chemistry for summer internship funding (H.-X.L.), Nankai
Percentages refer to isolated yields.
University College of Chemistry for an International Re-
search Scholarship (X.L.), and the A. P. Sloan Foundation and
formed C(sp3)@O bond. The stereochemistry of 7 b and 7 c Dreyfus Foundation for young faculty fellowships (K.M.E.).
We thank Joseph Derosa, Xin Wang, and Mingyu Liu for
was assigned by analogy assuming a syn-migratory insertion
event. One plausible stereoinduction model is shown in donation of alkene substrates. Dr. Jason Chen and Brittany
Table 5 (bottom left). In this model, the directing group binds Sanchez (Scripps Research Automated Synthesis Facility) are
in a bidentate fashion, displacing the phosphine ligand. The acknowledged for SFC and HRMS analysis. We further thank
bottom-facing methyl group then affects the preferred Dr. Milan Gembicky and Jake B. Bailey (UCSD) for X-ray
coordination mode of the alkene to the palladium center crystallographic analysis.
during the migratory insertion step through steric clashing.
Alternatively, the directing group could be bound in a mono-
dentate fashion, with the phosphine still coordinated (see SI Conflict of interest
for additional discussion).
The authors declare no conflict of interest.

Conclusion Keywords: alkene · borylation · carboboration · directing group ·

palladium
In conclusion, we have developed highly regio- and
diastereoselective carboboration and carbosilylation reac-
tions of alkenyl carbonyl compounds using a substrate How to cite: Angew. Chem. Int. Ed. 2019, 58, 17068 – 17073
Angew. Chem. 2019, 131, 17224 – 17229
directivity strategy. Compatible substrates include alkenes
with various substitution patterns and benzo-fused hetero-
aromatics that react through five- and six-membered pallada- [1] For reviews, see: a) M. Suginome, Chem. Rec. 2010, 10, 348 – 358;
cycle intermediates. These methods allow direct access to b) Z. Liu, Y. Gao, T. Zeng, K. M. Engle, Isr. J. Chem. 2019,
carbonyl products containing boron and silicon groups at the https://doi.org/10.1002/ijch.201900087.
b and g positions. Furthermore, an array of aryl and alkenyl [2] For examples of copper-catalyzed intermolecular 1,2-carbobo-
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