Efficient Access to Chiral β-Borylated Carboxylic Esters via Rh-Catalyzed Hydrogenation

Article abstract of DOI:10.1002/adsc.201900161

Rh/bisphosphine?thiourea ligand (ZhaoPhos)-catalyzed asymmetric hydrogenation of (Z)-β-substituted-β-boryl-α,β-unsaturated esters was successfully developed, furnishing a variety of chiral β-borylated carboxylic esters with high yields and excellent enantioselectivities (up to 99% yield and >99% ee). The gram-scale asymmetric hydrogenation was performed efficiently in the presence of only 0.05 mol% (S/C=2 000) catalyst loading with full conversion, 99% yield and 99% ee. Moreover, the hydrogenation product was easily converted to other versatile synthetic intermediates, such as methyl (S)-3-hydroxy-3-phenylpropanoate and methyl (S)-3-(furan-2-yl)-3-phenylpropanoate. (Figure presented.).

Full text of DOI:10.1002/adsc.201900161

Title: Efficient Access to Chiral β-Borylated Carboxylic Esters via Rh-
Catalyzed Hydrogenation
Authors: Gang Liu, Anqi Li, Xueyuan Qin, Zhengyu Han, Xiu-Qin Dong,
and Xumu Zhang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900161
Link to VoR: http://dx.doi.org/10.1002/adsc.201900161

10.1002/adsc.201900161
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Efficient Access to Chiral β-Borylated Carboxylic Esters via
Rh-Catalyzed Hydrogenation
Gang Liu,† Anqi Li,† Xueyuan Qin,† Zhengyu Han,† Xiu-Qin Dong,*† Xumu Zhang*‡
† Key Laboratory of Biomedical Polymers, Engineering Research Center of Organosilicon Compounds & Materials,
Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, P. R.
China.
‡ Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen,
Guangdong, 518055, P. R. China.
E-mail address: zhangxm@sustc.edu.cn; xiuqindong@whu.edu.cn.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
hydrogenation is a straightforward, efficient and high
atom-economic method with great practical potential
for the synthesis of chiral compounds.[11] Based on
our long-standing efforts in the research field of
asymmetric hydrogenation, we are interested in the
exploration of highly efficient synthetic methods to
prepare chiral organoboron compounds. Inspired by
the excellent performance of the bifunctional
Abstract. Rh/bisphosphine-thiourea ligand (ZhaoPhos)-
catalyzed asymmetric hydrogenation of (Z)-β-substituted-β-
boryl-α,β-unsaturated esters was successfully developed,
furnishing a variety of chiral β-borylated carboxylic esters
with high yields and excellent enantioselectivities (up to
99% yield and >99% ee). The gram-scale asymmetric
hydrogenation was performed efficiently in the presence of
only 0.05 mol% (S/C = 2 000) catalyst loading with full
conversion, 99% yield and 99% ee. Moreover, the
hydrogenation product was easily converted to other
versatile synthetic intermediates, such as methyl (S)-3-
hydroxy-3-phenylpropanoate and methyl (S)-3-(furan-2-
yl)-3-phenylpropanoate.
bisphosphine-thiourea
ligand
(ZhaoPhos)
in
asymmetric hydrogenation utilizing the possible
interactions between the thiourea scaffold and the
functional group of substrates,[12] we herein report
asymmetric hydrogenation of (Z)-β-substituted-β-
boryl-α,β-unsaturated esters to afford chiral β-
borylated carboxylic esters with high reactivity and
excellent enantioselective control (Scheme 1, up to
99% yield, >99% ee). In addition, the gram-scale
asymmetric hydrogenation was proceeded well even
with only 0.05 mol% catalyst loading (S/C = 2 000),
and the hydrogenation product was easily converted
to other chiral building blocks through simple organic
transformations.
Keywords: Asymmetric hydrogenation, β-boryl-α,β-
unsaturated esters, chiral β-borylated carboxylic esters,
enantioselectivity, bisphosphine ligand.
The α-chiral boron compounds have been
recognized as an important class of organoboron
compounds, which occupied a unique position in the
field of asymmetric synthesis.[1] They have been
widely served as versatile precursors to access chiral
C−O, C−N, and C−C bonds with the retention of
enantiopurity.[2] In addition, they are attractive
building blocks for the construction of a variety of
useful functionalized molecules.
An increasing effort has been devoted to
developing efficient enantioselective methods to
Scheme 1. Preparation of chiral β-borylated carboxylic
esters through Rh-catalyzed asymmetric hydrogenation.
construct
these
organoboron
compounds,[3-9]
The initial research for [Rh(nbd)2]BF4-catalyzed
asymmetric hydrogenation of model substrate ethyl
(Z)-3-phenyl-3-(4, 4, 5, 5-tetramethyl-1, 3, 2-
dioxaborolan-2-yl) acrylate 1a[13] was begun to
investigate the solvent effect using the ZhaoPhos L1
as the ligand under 50 atm H2 at 30 °C. As shown in
Table 1, moderate to good reactivities and
enantioselectivities were obtained in MeOH and
including metal-catalyzed[3] and metal-free[4]
asymmetric boron conjugate additions to α,β-
unsaturated esters and derivatives, enantioselective
borylation of alkenes and alkynes,[5-6] lithiation-
borylation reactions,[7] asymmetric hydrogenation,[8]
kinetic resolution of β-borylated carboxylic esters[9]
and selective oxidation of boronates[10]. It is well-
known that transition-metal-catalyzed asymmetric
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900161
Advanced Synthesis & Catalysis
CHCl3 (68%-80% conversions, 77%-85% ee, Table of ligand L4 with urea motif and ligand L5
1, entries 1, 7). To our delight, high conversions and
excellent enantioselectivities can be achieved in
without thiourea group (67%-69% conversions,
15%-32% ee, Table 2, entries 4-5). Other
important chiral bisphosphine ligands, such as
(S)-BINAP, (S)-SegPhos and (Rc, Sp)-DuanPhos,
trifluoroethanol
(TFE),
hexafluoroisopropanol
(HFIP), dichloromethane (DCM), toluene and hexane
(96%->99% conversions, 91%-95% ee, Table 1, almost did not promote this asymmetric
entries 2-6). Among these solvents, DCM provided
the best result (>99% conversion, 95% ee, Table 1,
entry 4). In addition, this asymmetric hydrogenation
can be finished in DCM when the reaction time was
reduced from 12 h to 6 h (Table 1, entry 8).
Moreover, other metal precursors, such as
[Rh(cod)2]BF4, [Rh(cod)Cl]2 and [Ir(cod)Cl]2, were
also applied in this asymmetric hydrogenation. Full
conversion and excellent enantioselectivity was
obtained with [Rh(cod)2]BF4 as the metal precursor
(>99% conversion, 93% ee, Table 1, entry 9). We
found that the [Ir(cod)Cl]2 is not suitable to work in
this asymmetric transformation, and very poor result
was afforded (Table 1, entry 11).
hydrogenation (Table 2, entries 6-8).
Table 2. Screening ligands for the Rh-catalyzed
asymmetric hydrogenation of ethyl (Z)-3-phenyl-3-(4,
4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) acrylate
(
1a).[a]
entry
ligand
conv. (%)[b]
Ee (%)[c]
1
2
3
4
5
6
7
8
ZhaoPhos L1
>99
>99
>99
69
95
41
86
32
15
NA
NA
NA
L2
L3
L4
Table 1. Screening solvents and metal precursors for the
asymmetric hydrogenation of ethyl (Z)-3-phenyl-3-(4, 4, 5,
5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) acrylate (1a).[a]
L5
67
(S)-BINAP
(S)-SegPhos
(Rc, Sp)-DuanPhos
trace
trace
trace
[a] Unless otherwise noted, all reactions were carried out
with a [Rh(nbd)2]BF4/ligand/substrate 1a (0.1 mmol) ratio
of 1:1.1:100 in 1.0 mL DCM under 50 atm H2 at 30 °C.
NA = not available.
entry
metal
precursor
solvent time conv.
ee
(h)
(%)[b] (%)[c]
[b] Conversion was determined by 1H NMR analysis.
[c] Ee was determined by chiral HPLC analysis.
1
2
3
4
5
6
7
8
9
[Rh(nbd)2]BF4 MeOH
12
12
12
12
12
12
12
6
80
>99
96
>99
>99
>99
68
>99
>99
57
85
92
91
95
93
93
77
95
93
90
NA
[Rh(nbd)2]BF4
[Rh(nbd)2]BF4
[Rh(nbd)2]BF4
[Rh(nbd)2]BF4 toluene
[Rh(nbd)2]BF4 hexane
[Rh(nbd)2]BF4 CHCl3
[Rh(nbd)2]BF4
[Rh(cod)2]BF4
[Rh(cod)Cl]2
[Ir(cod)Cl]2
TFE
HFIP
DCM
DCM
DCM
DCM
DCM
6
6
6
10
11
trace
[a] Unless otherwise noted, all reactions were carried out
with a metal precursor/ZhaoPhos L1/substrate 1a (0.1
mmol) ratio of 1:1.1:100 in 1.0 mL solvent under 50 atm
H2 at 30 °C. The catalyst was pre-complexed in DCM (0.1
mL for each reaction vial). The configuration of 2a was
determined by comparing the optical rotation data with
reported in the literature.[3d] NA = not available.
Figure 1. The structure of chiral diphosphine ligands.
With the optimized reaction conditions in hand,
great effort was deveoted to the exploration of the
substrate scope of the Rh-catalyzed asymmetric
hydrogenation of (Z)-β-substuituted-β-(4, 4, 5, 5-
[b] Conversion was determined by 1H NMR analysis.
[c] Ee was determined by chiral HPLC analysis.
tetramethyl-1,
3,
2-dioxaborolan-2-yl)-α,
β-
unsaturated esters. These reaction results were
summarized in Table 3. A variety of (Z)-β-aryl
substuituted-β-(4, 4, 5, 5-tetramethyl-1, 3, 2-
dioxaborolan-2-yl)-α, β-unsaturated esters were
hydrogenated smoothly with excellent results (>99%
A series of important chiral bisphosphine
ligands
[Rh(nbd)2]BF4-catalyzed
hydrogenation of ethyl (Z)-3-phenyl-3-(4, 4, 5, 5-
were
then
applied
into
this
asymmetric
tetramethyl-1, 3, 2-dioxaborolan-2-yl) acrylate 1a conversion, 96%-99% yields, 94%->99% ee). When
(Figure
1).
Among
these
bifunctional
L4 (Table 2,
the ethyl ester group was replaced with methyl, n-
propyl or i-propyl ester group, it had little effect on
the reactivity and enantioselectivity. And the
corresponding hydrogenation products (2a-2d) were
obtained with full conversions, 99% yield, 94%-99%
ee. In addition, a series of methyl β-substituted-β-(4,
bisphosphine-(thio)urea ligands L1
-
entries 1-4), ZhaoPhos L1 provided the best
results with full conversion and 95% ee (Table 2,
entry 1). Moderate conversions and poor
enantioselectivities were obtained in the presence
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900161
Advanced Synthesis & Catalysis
4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-α, β- enantioselectivity was obtained (82% conversion,
unsaturated esters bearing electron-rich (1e-1h), 49% ee). It indicated that ester group of substrate
electron-deficient (1i-1l), or electron-neutral (1m) is possible to form hydrogen-bonding interaction
groups on phenyl ring proceeded smoothly to afford with the thiourea motif of ligand, which is
the corresponding products chiral boronic esters (2e- important to obtain high reactivity and excellent
2m) in high yields (96%-99% yields) and excellent
enantioselectivities (95%->99% ee). The 2-napthyl
substituted substrate (1n) was hydrogenated
efficiently with 99% yield and 98% ee. To our
delight, the alkyl substrate methyl (Z)-3-cyclohexyl-
3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acryl-
ate (1o) also worked in this asymmetric
enantioselectivity in this hydrogenation.
hydrogenation,
high
yield
and
moderate
Scheme 2. Asymmetric hydrogenation of substrate 1p
without ester group.
enantioselectivity were obtained (99% yield, 55% ee).
Table 3. Substrate scope of Rh-catalyzed asymmetric
hydrogenation of (Z)-β-substituted-β-(4, 4, 5, 5-
tetramethyl-1, 3, 2-dioxaborolan-2-yl)-α, β-unsaturated
esters.[a]
The gram-scale Rh/ZhaoPhos L1-catalyzed
asymmetric hydrogenation of methyl (Z)-3-
phenyl-3-(4, 4, 5, 5-tetramethyl-1, 3, 2-
dioxaborolan-2-yl) acrylate (1b) proceeded well
even with only 0.05 mol% (S/C = 2 000) catalyst
loading. This hydrogenation was conducted at
100 atm H2 for better conversion, and the desired
hydrogenation product 2b was afforded with full
conversion, 99% yield and 99% ee (Scheme 3).
Scheme 3. Gram-scale asymmetric hydrogenation with
high TON.
Organoboronic esters are important and attractive
precursors in organic synthesis to provide highly
versatile organic molecules. As shown in Scheme 4,
the hydrogenation product 2b was easily oxidized by
NaBO3·4H2O to provide methyl (S)-3-hydroxy-3-
phenylpropanoate 3b with the conversion of carbon-
boron bond to carbon-oxygen bond in 90% yield 95%
ee.[2h] In addition, the methyl (S)-3-(furan-2-yl)-3-
phenylpropanoate 4b can be obtained through the
coupling reaction with furan in the presence of n-
BuLi and N-bromo succinimide (NBS) in 75% yield
and without loss of enantiopurity (99% ee).[14]
[a] Unless otherwise noted, all reactions were carried out
with a [Rh(nbd)2]BF4/ZhaoPhos L1/substrate 1 (0.1 mmol)
ratio of 1:1.1:100 in 1.0 mL CH2Cl2 under 50 atm H2 for 6
1
h at 30 °C. Conversions determined by H NMR analysis
of the crude reaction mixtures were >99%. Yields were
corresponded to isolated yields. Ee values were determined
by chiral HPLC analysis.
[b] 1.0 mol% catalyst loading, 40 atm H2, 6 h at 30 °C.
[c] The reaction was carried out at 40 °C for 12 h with 2.0
mol% catalyst loading.
Scheme 4. Synthetic transformations of chiral
organoboronic ester 2b.
In addition, the substrate 4,4,5,5-tetramethyl-2-
(1-phenylvinyl)-1,3,2-dioxaborolane 1p without
ester group was applied in this asymmetric
hydrogenation. As shown in Scheme 2, it was not
completely converted to product 2p, and poor
In summary, we have successfully developed a
new and efficient approach to access synthetically
valuable chiral organoboronic esters through
Rh/ZhaoPhos
L1-catalyzed
asymmetric
hydrogenation of
(Z)-β-substituted-β-boryl-α,β-
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900161
Advanced Synthesis & Catalysis
unsaturated esters with excellent results (up to 99%
yield and >99% ee). In addition, this asymmetric
hydrogenation methodology displayed high catalytic
activity, the gram-scale asymmetric hydrogenation
was performed efficiently even in the presence of
0.05 mol% (S/C = 2 000) catalyst loading with full
conversion, 99% yield and 99% ee. Moreover, the
chiral organoboronic esters have been emerged as
important and versatile functional groups, the
hydrogenation product was easily converted to other
versatile synthetic intermediates, such as methyl (S)-
3-hydroxy-3-phenylpropanoate and methyl (S)-3-
(furan-2-yl)-3-phenylpropanoate.
Chem. Soc. 2009, 131, 5024-5025; e) D. G. Hall,
Boronic Acids. Preparation, Applications in
Organic Synthesis and Medicine, Wiley-VCH,
Weinheim, 2005; f) H. K. Scott, V. K. Aggarwal,
Chem. Eur. J. 2011, 17, 13124-13132; g) C. M.
Crudden, D. Edwards, Eur. J. Org. Chem. 2003
,
4695-4712; h) Z. Niu, J. Chen, Z. Chen, M. Ma, C.
Song, and Y. Ma, J. Org. Chem. 2015, 80, 602-608.
[3] a) S. Kobayashi, P. Xu, T. Endo, M. Ueno, T.
Kitanosono, Angew. Chem. Int. Ed. 2012, 51,
12763-12766; b) J.-E. Lee and J. Yun, Angew.
Chem. Int. Ed. 2008, 47, 145-147; c) J.-B. Xie, S.
Lin, J. Luo, J. Wu, T. R. Winn and G. Li, Org.
Chem. Front. 2015, 2, 42-46; d) K. Toribatake, L.
Zhou, A. Tsuruta, H. Nishiyama; Tetrahedron
2013, 69, 3551-3560; e) J. K. Park, H. H. Lackey,
M. D. Rexford, K. Kovnir, M. Shatruk, and D. T.
McQuade, Org. Lett. 2010, 12, 5008-5011; f) J.-L.
Zhang, L.-A. Chen, R.-B. Xu, C.-F. Wang, Y.-P.
Ruan, A.-E. Wang, P.-Q. Huang, Tetrahedron:
Asymmetry 2013, 24, 492-498; g) V. Lillo, A.
Prieto, A. Bonet, M. M. Díaz-Requejo, E.
Fernández, Organometallics, 2009, 28, 659-662; h)
J. M. O’Brien, K. Lee, and A. H. Hoveyda, J. Am.
Chem. Soc. 2010, 132, 10630-10633.
Experimental Section
General procedure for the asymmetric hydrogenation
with S/C = 100: In the argon-filled glovebox, a solution of
ZhaoPhos (9.6 mg, 0.011 mmol) and [Rh(nbd)2]BF4 (3.75
mg, 0.01 mmol) in 1.0 mL anhydrous CH2Cl2 was stirred
at room temperature for 30 min. 100 μL of the resulting
solution was transferred by syringe into a vial charged with
1 (0.1 mmol) in 1.0 mL anhydrous CH2Cl2. The vials were
transferred to an autoclave, which was then charged with
50 atm of H2 and stirred at 30 °C for 6 h. The hydrogen
gas was released slowly and the solution was concentrated
and passed through a short column of silica gel to remove
the metal complex. The crude product was analyzed by 1H
NMR analysis for conversion (always >99%) and by chiral
HPLC for detremination of the enantiomeric excess before
purification by flash silica gel chromatography to isolate
the final product.
[4] H. Wu, S. Radomkit, J. M. O’Brien, A. H. Hoveyda,
J. Am. Chem. Soc. 2012, 134, 8277-8285.
[5] a) D. Noh, S. K. Yoon, J. Won, J. Y. Lee, J. Yun,
Chem. Asian J. 2011, 6, 1967-1969; b) H. M.
Nelson, B. D. Williams, J. Mirꢀ, F. D. Toste, J. Am.
Chem. Soc. 2015, 137, 3213-3216; c) J. R. Smith,
B. S. L. Collins, M. J. Hesse, M. A. Graham, E. L.
Acknowledgements
Myers, V. K. Aggarwal, J. Am. Chem. Soc. 2017
,
We are grateful for financial support from the National
Natural Science Foundation of China (Grant No. 21432007,
21502145), the Wuhan Morning Light Plan of Youth Science and
Technology (Grant No. 2017050304010307), the Fundamental
Research Funds for Central Universities (Grant No.
2042018kf0202), Shenzhen Nobel Prize Scientists Laboratory
Project (Grant No. C17783101), Science and Technology
139, 9148-9151; d) Y. Cai, X.-T. Yang, S.-Q.
Zhang, F. Li, Y.-Q. Li, L.-X. Ruan, X. Hong, S.-L.
Shi, Angew. Chem. Int. Ed. 2018, 57, 1376-1380; e)
H. Iwamoto, T. Imamoto, H. Ito, Nature Commun.
2018, 9, 2290-2299.
[6] J. Guo, B. Cheng, X. Shen, Z. Lu, J. Am. Chem.
Soc. 2017, 139, 15316-15319.
[7] a) S. Nave, R. P. Sonawane, T. G. Elford, V. K.
Aggarwal, J. Am. Chem. Soc. 2010, 132, 17096-
17098; b) V. Bagutski, A. Ros, V. K. Aggarwal,
Tetrahedron 2009, 65, 9956-9960.
Innovation
Committee
of
Shenzhen
(Grant
No.
KQTD20150717103157174, JSGG 20170821140353405 and
JSGG 20160608140847864). The Program of Introducing
Talents of Discipline to Universities of China (111 Project) is
also appreciated.
[8] For some selected examples, see: a) M. Ueda, A.
References
Saitoh, N. Miyaura, J. Organomet. Chem. 2002
,
642, 145-147; b) J. B. Morgan, J. P. Morken, J.
Am. Chem. Soc. 2004, 126, 15338-15339; c) W. J.
Moran, J. P. Morken, Org. Lett. 2006, 8, 2413-
2415; d) A. Paptchikhine, P. Cheruku, M. Engman,
P. G. Andersson, Chem. Commun. 2009, 5996-
5998; e) J. Mazuela, P.-O. Norrby, P. G.
Andersson, O. Pꢁmies, M. Diꢂguez, J. Am. Chem.
Soc. 2011, 133, 13634-13645; f) A. Ganiꢃ, A.
Pfaltz, Chem.-Eur. J. 2012, 18, 6724-6728; g) M.
Biosca, A. Paptchikhine, O. Pꢁmies, P. G.
Andersson, M. Diꢂguez, Chem.-Eur. J. 2015, 21,
3455-3464.
[1] For some selected reviews: a) H. C. Brown, B.
Singaram, Acc. Chem. Res. 1988, 21, 287-293; b)
H. C. Brown, V. P. Ramachandran, Pure Appl.
Chem. 1991, 63, 307-316; c) H. C. Brown, V. P.
Ramachandran, J. Organomet. Chem. 1995, 500,
1−19; d) C. M. Crudden, B. W. Glasspoole, C. J.
Lata, Chem. Commun. 2009, 6704-6716; e) C.
Sandford, V. K. Aggarwal, Chem. Commun. 2017
53, 5481-5494.
,
[2] a) B. S. L. Collins, C. M. Wilson, E. L. Myers, V.
K. Aggarwal, Angew. Chem. Int. Ed. 2017, 56,
11700-11733; b) J. L. Stymiest, V. Bagutski, R. M.
French, V. K. Aggarwal, Nature 2008, 456, 778-
782; c) J. C. H. Lee, D. G. Hall, J. Am. Chem. Soc.
2010, 132, 5544-5545; d) D. Imao, B. W.
Glasspoole, V. S. Laberge, C. M. Crudden, J. Am.
[9] J. S. Reis, L. H. Andrade, Tetrahedron: Asymmetry
2012, 23, 1294-1300.
[10] a) P. B. Brondani, G. de Gonzalo, M. W. Fraaije,
L. H. Andrade, Adv. Synth. Catal. 2011, 353,
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900161
Advanced Synthesis & Catalysis
2169-2173; b) P. B. Brondani, H. Dudek, J. S.
Reis, M. W. Fraaije, L. H. Andrade, Tetrahedron:
Asymmetry 2012, 23, 703-708.
[11] Selected examples: a) W. Tang, X. Zhang, Chem.
Rev. 2003, 103, 3029-3070; b) J.-H. Xie, S.-F.
Zhu, Q.-L. Zhou, Chem. Rev. 2011, 111, 1713-
1760; c) J.-H. Xie, Q.-L. Zhou, Acta Chim. Sinica
2012, 70, 1427-1438; d) S.-F. Zhu, Q.-L. Zhou,
Acc. Chem. Res. 2017, 50, 988-1001; e) Z. Zhang,
N. A. Butt, W. Zhang, Chem. Rev. 2016, 116,
14769-14827; f) D.-S. Wang, Q.-A. Chen, S.-M.
Lu, Y.-G. Zhou, Chem. Rev. 2012
,
112,
2557−2590; g) S. J. Roseblade, A. Pfaltz, Acc.
Chem. Res. 2007, 40, 1402-1411; h) G. Erre, S.
Enthaler, K. Junge, S. Gladiali, M. Beller, Coord.
Chem. Rev. 2008, 252, 471-491; i) T. L. Church, P.
G. Andersson, Coord. Chem. Rev. 2008, 252, 513-
531; j) J. J. Verendel, O. Pꢁmies, M. Diꢂguez, P.
G. Andersson, Chem. Rev. 2014, 114, 2130-2169.
[12] Selected examples: a) Q. Zhao, S. Li, K. Huang, R.
Wang and X. Zhang, Org. Lett. 2013, 15, 4014-
4017; b) P. Li, M. Zhou, Q. Zhao, W. Wu, X. Hu,
X.-Q. Dong and X. Zhang, Org. Lett. 2016, 18, 40-
43; c) Q. Zhao, J. Wen, R. Tan, K. Huang, P.
Metola, R. Wang, E. V. Anslyn and X. Zhang,
Angew. Chem. Int. Ed. 2014, 53, 8467-8470; d) J.
Wen, R. Tan, S. Liu, Q. Zhao and X. Zhang, Chem.
Sci. 2016, 7, 3047-3051; e) Z. Han, P. Li, Z. Zhang,
C. Chen, Q. Wang, X.-Q. Dong and X. Zhang,
ACS Catal. 2016, 6, 6214-6218; f) T. Zhang, J.
Jiang, L. Yao, H. Geng, X. Zhang, Chem. Commun.
2017, 53, 9258-9261; g) G. Liu, Z. Han, X.-Q.
Dong, X. Zhang, Org. Lett. 2018, 20, 5636-5639.
[13] a) C. L. Peck, J. A. Calderone, W. L. Santos,
Synthesis 2015, 47, 2242-2248; b) J. Lee, J. Kwon
and J. Yun, Chem. Commun. 2008, 733-734.
[14] M. Odachowski, A. Bonet, S. Essafi, P. Conti-
Ramsden, J. N. Harvey, D. Leonori, and V. K.
Aggarwal, J. Am. Chem. Soc. 2016, 138, 9521-
9532.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900161
Advanced Synthesis & Catalysis
COMMUNICATION
Efficient Access to Chiral β-Borylated Carboxylic
Esters via Rh-Catalyzed Hydrogenation
Adv. Synth. Catal. 2019, Volume, Page – Page
Gang Liu,† Anqi Li,† Xueyuan Qin,† Zhengyu Han,†
Xiu-Qin Dong,*† Xumu Zhang*‡
6
This article is protected by copyright. All rights reserved.