Copper-Catalyzed Alkynylboration of Alkenes with Diboron Reagents and Bromoalkynes

Article abstract of DOI:10.1002/asia.201701176

An efficient method for the synthesis of homopropargylboronates by copper-catalyzed alkynylboration of alkenes with diboron reagents and bromoalkynes has been developed. The alkynylboration reaction features high selectivity and efficiency, mild reaction conditions, wide substrate scope, and functional-group compatibility, and is a highly attractive complement to existing methods for the synthesis of homopropargylboronates. Both the boryl and alkynyl groups are good potential functional groups for the subsequent manipulations that provide access to a variety of important molecule structures.

Full text of DOI:10.1002/asia.201701176

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Copper-Catalyzed Alkynylboration of Alkenes with Diboron
Reagents and Bromoalkynes
Authors: Tian-Jun Gong, Shang-Hai Yu, Kuan Li, Wei Su, Xi Lu, Bin
Xiao, and Yao Fu
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: Chem. Asian J. 10.1002/asia.201701176
Link to VoR: http://dx.doi.org/10.1002/asia.201701176
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201701176
Chemistry - An Asian Journal
DOI: 10.1002/anie.201((will be filled in by the editorial staff))
Cross-Coupling
Copper-Catalyzed Alkynylboration of Alkenes with Diboron Reagents
and Bromoalkynes**
Tian-Jun Gong, Shang-Hai Yu, Kuan Li, Wei Su, Xi Lu, Bin Xiao,* and Yao Fu*
Abstract: A new and efficient method for the synthesis of
homopropargylboronates by copper-catalyzed alkynylboration of
alkenes with diboron reagents and bromoalkynes has been
developed. The alkynylboration reaction features high selectivity
and efficiency, mild reaction conditions, wide substrate scope, and
Considering that homopropargylboronates are important functional
groups in organic synthesis, which provide efficient access to
homopropargylalcohol, homopropargylamine and heterocycles,[8]
the development of efficient methods for synthesis of
homopropargylboronates is highly demanded.
functional-group compatibility, and is
a
highly attractive
Herein, we report an example of copper-catalyzed regioselective
and enantioselective alkynylboration of alkenes with diboron
reagents and bromoalkynes (Scheme 1). This reaction presents a
efficient route to construct C(sp)-C(sp3) and C(sp3)-B bond in a
single step,[ 9-10] and tolerates a broad range of substituted alkenes
(styrenes, allene and 1,3-enyne) and bromoalkynes (silyl, aryl and
aliphatic alkynylbromides). Both the boryl and alkynyl groups can
be subsequent manipulations provide efficient access to a variety of
high-value products.
complement to existing methods for the synthesis of
homopropargylboronates. Both the boryl and alkynyl groups are
good potential functional groups, for the subsequent manipulations
which provide an efficient access to a variety of important molecule
structures.
Alkylboronic acid derivatives are versatile intermediates in
organic synthesis,[1a] and also as interesting compounds in medicinal
chemistry (e.g., bortezomib).[1h] The development of new methods
to synthesize alkylboronic acid derivatives has been intensively
studied in organic chemistry.[2-7] Transition-metal-catalyzed
boration/functionalization of C-C double bonds has been established
as an important strategy for the expedient synthesis of complex and
reactive boron-containing compounds from readily available starting
materials in a single step.[4-7] One main feature of the process of
boration/functionalization is that, in addition to generating the
alkylboronates motif, a synthetically versatile group (e.g., boryl,[5d,
5g]
7i, 7n]
7f]
amino,[5k-m] aryl,[7b-d,
alkyl,[6,
alkenyl[7c]
) is also
incorporated. For instance, Hoveyda et al. realized the
copper-catalyzed carboboration of alkenes (1, 3-enynes and 1,
8a]
3-dienes) with B2pin2 and aldehydes, aldimines or enoate[7j,
.
Brown and Nakao et al., independently, reported synergistic
Pd/Cu-catalyzed intermolecular arylboration reactions of
vinylarenes, in which C(sp3)-B and C(sp3)-C(sp2) bond formation
were realized. Liao reported a Cu/Pd cooperative catalysis for
enantioselective allylboration of alkenes.[7e] More recently, our
group reported an example of ligand-controlled regiodivergent
copper-catalyzed alkylboration of unactivated alkenes.[7f] Despite of
these pioneering excellent examples of boration/functionalization of
alkenes, alkynylboration of alkenes has never been reported.
Scheme 1. Cu(I)-Catalyzed Alkynylboration of Alkenes.
We initially used 4-vinylbiphenyl, bis(pinacolato)diboron
(pinB-Bpin) and triisopropylsilylethynyl bromide as model
substrates to attempt the alkynylboration reaction. After extensive
screening of various reaction parameters, we were pleased to find
that the alkynylboration occurred in the presence of a CuCl/PCy3
catalyst and a LiOtBu base in THF at room temperature, and the
desired product 3a was obtained in 34% isolated yield. The yield
was not improved when DPPBz was used. With IMes·HCl as
ligands, excellent yields of 3a were obtained (entry 3). While
ICy·HCl gave moderate yields, only 6% yield of product was
obtained when bulky IPr·HCl was used as ligand (entry 5).
Moreover, when we used IMesCuCl instead of CuCl and IMes·HCl,
the yield of 3a was slightly improved (entry 6). The effects of
various bases on the reaction was also tested , whereas other bases
such as NaOtBu, KOtBu, KOTMS and Cs2CO3 afforded the desired
product in moderate yields (See SI). When triisopropylsilylethynyl
chloride was used instead of triisopropylsilylethynyl bromide, a
much lower yield of 3a was obtained (entry 7), while
triisopropylsilylethynyl iodine provide only trace amounts of desired
[]
Tian-Jun Gong,† Shang-Hai Yu,† Kuan Li, Wei Su, Xi Lu, Bin Xiao,
and Yao Fu
Hefei National Laboratory for Physical Sciences at the Microscale,
iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui
Province Key Laboratory of Biomass Clean Energy, University of
Science and Technology of China, Hefei.
Email: binxiao@ustc.edu.cn; fuyao@ustc.edu.cn
[†]
These authors contributed equally to this work.
[]
We thank the support from National Natural Science Foundation of
China (21325208, 21572212, 21502184), Ministry of Science and
Technology of China (2017YFA0303500), Chinese Academy of
Science (XDB20000000), Key Technologies R&D Programme of
Anhui Province (1604a0702027), FRFCU and PCSIRT.
Table 1: Optimization of Reaction Conditions.[a]
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
1
This article is protected by copyright. All rights reserved.

10.1002/asia.201701176
Chemistry - An Asian Journal
product (entry 8). Lower yield of product was obtained when 1.5
equivalents of alkynyl bromide was used (entry 9). In all the above
reactions, this reaction performed excellent regio-selectivity.
With the optimized conditions identified, we first investigated
the scope of bromoalkynes (Scheme 2). A variety of silylated
alkynylbromides were well tolerated in this reaction (3a-3d). In
addition to silylated alkynylbromides, the reaction proceeded well
with aryl and aliphatic alkynylbromides bearing different functional
groups, giving products bearing a phenyl group (3f, 68% yield) or
benzyl-protected propargylic alcohols (3h, 73%). We were surprised
to find that a steroid group, useful biologically active compounds,
can smoothly survive the alkynylboration process (3k). Other
diboron reagents, such as bis(neopentyl glycolato)diboron and
bis[(+)-pinanediolato]diboron, can also be applied in the reaction
with acceptable yields. Then, we tested the scope of styrenes. As to
the electronic effects of the substituents on the reaction, both
electron-donating (3m) and withdrawing groups (3n) could be
tolerated. The fluoro-containing groups that are frequently found in
agrochemical and pharmaceutical products were well compatible
with the alkynylboration processes (3o, 3p). Moreover, the
aryl-halogen (Cl, Br) and OTs groups were well tolerated in the
alkynylboration reaction (3q-s), which made additional
functionalization possible at these positions. For a di-vinyl substrate,
we can obtain the product 3u carrying a vinyl group by using 1.5
equivalent B2pin2 and 2 equivalent bromoalkyne. As for the
substrates containing an indole (3v) or benzothiophene (3w), the
present reaction occurred smoothly. In addition, sterically hindered
styrenes such as ortho-Me (3x) and ortho-OMe (3y) styrene posed
no problem during the cross-coupling process. α-Quaternary
homopropargyl-
entry
X
Br
Br
Br
Br
Br
Br
Cl
I
Ligand+Cat.[Cu]
Base
LiOtBu
Yield (%) [b]
1
2
3
4
5
6
7
8
9c
PCy3 + CuCl
DPPBz + CuCl
IMes·HCl + CuCl
ICy·HCl + CuCl
IPr·HCl + CuCl
IMesCuCl
34
12
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
85
57
6
90
IMesCuCl
60
IMesCuCl
Trace
81
Br
IMesCuCl
[a] Reaction conditions: alkene 1a (0.1 mmol), (Bpin)2 (0.15 mmol),
haloalkynes 2 (0.2 mmol), CuCl (0.01 mmol), ligand (0.011 or 0.022
mmol), and LiOtBu (0.2 mmol) were stirr in THF (0.5 mL) at room
temperature for 12 h. [b] Isolated yield of pure 3a. [c] haloalkynes 2
(0.15 mmol). B2pin2 = bis(pinacolato)diboron.
2
This article is protected by copyright. All rights reserved.

10.1002/asia.201701176
Chemistry - An Asian Journal
Scheme 2: Substrate Scope. [a] Reaction conditions: alkenes (0.1 mmol), B2pin2 (0.15 mmol), haloalkynes (0.2 mmol), IMesCuCl (0.01
mmol), and LiOtBu (0.2 mmol) were stirr in THF (0.5 mL) at room temperature for 12 h. Isolated yields of pure 3 or 4 are shown. [b]
Bis(neopentyl glycolato)diboron (0.15 mmol) was used instead of B2pin2. [c] Bis[(+)-pinanediolato]diboron (0.15 mmol) was used instead of
B2pin2。[d] Cs2CO3 (0.2 mmol) was used instead of LiOtBu. [e] KOtBu (0.2 mmol) was used instead of LiOtBu. [f] NaBO3·4H2O, THF/H2O,
rt., 4h. B2pin2 = bis(pinacolato)diboron.
boronate can be obtained by alkynylboration with sterically hindered
1,1-disubstituted alkenes (3z), which is difficult to obtained by Ito’s
hydroboration of an enyne.[8b] To our delight, macrocyclic alkyne
could be synthesized from intramolecular alkynylboration (3aa). It
presents the first example of macro-sized-ring synthesis in
carboboration. In line with the expected reaction result,
1,2-disubstituted alkene and alkyl-substituted alkenes are ineffective
substrates.
Au(PPh3)3Cl, AgSbF6, TsOH·H2O, MeOH, r. t.; [g] Ni(cod)2, CsF,
ZnMe2, CO2 balloon, 60 °C.
/AgSbF6catalyzed endo-cyclization reaction, the tetrahydrofuran
derivatives was obtained in 67% yield (9).[12d] Moreover,
γ-butyrolactones derivatives can be obtained by using Ni-catalyzed
exo-cyclization reaction (10).[12e] Thus, the Cu-catalyzed
alkynylboration of alkenes is synthetically useful and the
homoalkynylboronic esters products can be readily converted to
diverse useful molecules.
Inspired by the high efficiency of this reaction, we applied the
present protocol to catalytic enantioselective alkynylboration by
using an appropriate optically active ligand (Scheme 4, See SI).
Alkynylboration of 1, 1-disubstituted alkenes with 2a in the
presence of NHC precursor afforded the α-quaternary
homopropargylboronate in 44% yield with 92.9:7.1 er.[13] It provides
an efficient method to construct chiral quaternary carbon.
Besides styrenes, other types of alkenes were also examined in
this reaction. Gratifyingly, when oxabenzonorbornadiene was used
as alkene for the alkynylboration, the reaction proceeded smoothly
without the formation of ring-opened side products (4a, 4b), which
were consistent with the recent work of Miura and co-workers.[5l]
Furthermore, terminal vinyl silane also underwent the
alkynylboration reaction to provide the desired product in 40% yield
(4c). To be pointed out that, silicon compounds are very important
synthetic reagents and intermediates in modern organic synthesis.
When cyclohexyl allene was used, the product was obtained in 51%
yield (4d). Interestingly, when 1,3-enyne was used as alkene for the
alkynylboration,[11] 1,4-alkynylboration product was obtained (Eq.1,
Scheme 4. Preliminary Results of Enantioselective Alkynylboration.
To study the mechanism of the alkynylboration of alkenes, we
sought to gain evidence for the possible reactive intermediates
involved in the reaction (Scheme 5). When alkynylborane (11) was
subjected to the optimized reaction conditions for 4-vinylbiphenyl,
3a was not produced.[14] Then, bis(borylated) derivative (12) was
subjected to the reaction, without obtaining the 3a. These
observations exclude the possibility that bis(borylated) or
alkynylborane derivatives were intermediates in the alkynylboration
of alkenes. [15]
4e).
As
a
comparison,
3,4-carboboration[8a]
and
3,4-hydroboration[8b, c] to 1,3-enynes is the most common reaction
pattern .
Gram-scale syntheses of 3a and 3e were also carried out to test
the scalability of the transformation: The alkynylboration of 1a on a
3.0 mmol scale afforded 3a and 3e in 80% yield and 68% yield,
respectively, with 2 mol% catalyst loading. We then demonstrated
the versatility of the alkynylboration products (Scheme 6). These
products could be efficiently converted into 4-biphenyl-3-butyn-1-ol
(5) at 80% yield in two steps. This terminal alkynes can further
transformed to heteroaryl ring under Click reaction and Sonogashiya
reaction conditions (6, 7).[12a,b] The boronic esters can be easily
transformed to amine (8),[12c] while homopropargylamines are useful
building blocks in organic synthesis. By oxidation and Au(PPh3)2Cl2
Scheme 5. Mechanistic Insights.
On the basis of these experiments,
a possible reaction
mechanism was proposed (Scheme 6). First, IMesCuOtBu complex
was generated from the reaction of IMesCuCl and LiOtBu. Then
σ-bond metathesis with pinB-Bpin generates borylcopper species I.
Subsequent insertion of the alkene into the Cu-B bond of I furnishes
a borylated alkylcopper intermediate II.[16] Akynylation with the
bromoalkyne then occurs, which forms the desired alkynylboration
product along with the regeneration of the Cu(I) catalyst. As for
1,3-enyne, 1,3-isomerization of the propargylcopper III affording an
allenylcopper intermediate IV,[8a, 11] then oxidative addition with the
bromoalkyne to form intermediate V, which undergoes a reductive
elimination to furnish the target product.
Scheme 3. Transformations of Alkynylboration Products. [a]
NaBO3·4H2O, THF/H2O, r. t.; [b] TBAF, THF, r. t.; [c]
CuSO4·5H2O, BnN3, N2H4·H2O, r. t.; [d] Pd(PPh3)2Cl2, CuI,
2-bromophenol, NEt3, 90 °C; [e] BCl3, BnN3, DCM, r. t.; [f]
In summary, we have reported the an example of
copper-catalyzed regioselective alkynylboration of alkenes for
synthesis of homopropargylboronates. This protocol provides an
effective means to access an array of synthetically versatile building
3
This article is protected by copyright. All rights reserved.

10.1002/asia.201701176
Chemistry - An Asian Journal
3764; g) S. N. Mlynarski, C. H. Schuster, J. P. Morken, Nature 2014,
505, 386; h) L. Zhang, Z. Zuo, X. Leng, Z. Huang, Angew. Chem. Int.
Ed. 2014, 53, 2696; i) T. Itoh, T. Matsueda, Y. Shimizu, M. Kanai,
Chem. Eur. J. 2015, 21, 15955; j) T. Jia, P. Cao, D. Wang, Y. Lou, J.
Liao, Chem. Eur. J. 2015, 21, 4918; k) N. Matsuda, K. Hirano, T.
Satoh, M. Miura, J. Am. Chem. Soc. 2013, 135, 4934; l) R. Sakae, K.
Hirano, T. Satoh, M. Miura, Angew. Chem. Int. Ed. 2015, 54, 613; m)
K. Kato, K. Hirano, M. Miura, Angew. Chem. Int. Ed. 2016, 55, 14400;
n) X. Jia, Z. Huang, Nat. Chem. 2016, 8,157.
blocks that can be easily transformed into a variety of important
molecules. Chiral α-quaternary homopropargylboronate was
obtained by using hindered 1, 1-disubstituted alkene. this reaction
provides an efficient method to construct chiral quaternary carbon.
Moreover, this reaction presents the first example of
macro-sized-ring synthesis in carboboration.
(6) For selected examples of intramolecular carboboration of alkenes, see:
a) H. Ito, Y. Kosaka, K. Nonoyama, Y. Sasaki, M. Sawamura, Angew.
Chem., Int. Ed. 2008, 47, 7424; b) H. Ito, T. Toyoda, M. Sawamura, J.
Am. Chem. Soc. 2010, 132, 5990; c) C. Zhong, S. Kunii, Y. Kosaka, M.
Sawamura, H. Ito, J. Am. Chem. Soc. 2010, 132, 11440; d) A. R. Burns,
J. S. Gonzalez, H. W. Lam, Angew. Chem., Int. Ed. 2012, 51, 10827; e)
K. Kubota, E. Yamamoto, H. Ito, J. Am. Chem. Soc. 2013, 135, 2635.
(7) For selected examples of intermolecular carboboration of alkenes, see:
a) H. Yoshida, I. Kageyuki, K. Takaki, Org. Lett. 2013, 15, 952; b) K.
Semba, Y. Nakao, J. Am. Chem. Soc. 2014, 136, 7567; c) K. B. Smith,
K. M. Logan, W. You, M. K. Brown, Chem. Eur. J. 2014, 20, 12032;
d) K. M. Logan, K. B. Smith, M. K. Brown, Angew. Chem., Int. Ed.
2015, 54, 5228; e) T. Jia, P. Cao, B. Wang, Y. Lou, X. Yin, M. Wang, J.
Liao, J. Am. Chem. Soc., 2015, 137, 13760; f) W. Su, T.-J. Gong, X. Lu,
M.-Y. Xu, C.-G. Yu, Z.-Y. Xu, H.-Z. Yu, B. Xiao, Y. Fu, Angew.
Chem., Int. Ed. 2015, 54, 12957; g) Y. Yang, S. L. Buchwald, Angew.
Chem. Int. Ed. 2014, 53, 8677; h) Y. Yang, Angew. Chem. Int. Ed.
2016, 55, 345; i) K. Semba, Y. Ohtagaki, Y. Nakao, Org. Lett. 2016, 18,
3956; j) X. Li, F. Meng, S. Torker, Y. Shi, A. H. Hoveyda, Angew.
Chem., Int. Ed. 2016, 55, 9997; k) L. Jiang, P. Cao, M. Wang, B. Chen,
B. Wang, J. Liao, Angew. Chem. Int. Ed. 2016, 55, 13854; l) K. Yang,
Q. Song, Org. Lett. 2016, 18, 5460; m) K. Yang, Q. Song, J. Org.
Chem. 2016, 81, 1000; n) K. B. Smith, M. K. Brown, J. Am. Chem. Soc.
2017, 139, 7721; o) H. M. Nelson, B. D. Williams, J. Miro, F. D. Toste,
J. Am. Chem. Soc. 2015, 137, 3213.
Scheme 6. Possible Reaction Mechanism.
Received: ((will be filled in by the editorial staff))
Published online on ((will be filled in by the editorial staff))
Keywords: boration • synthetic methods • copper • difunctionalization
• cross-coupling
(8) a) F. Meng, F. Haeffner, A. H. Hoveyda, J. Am. Chem. Soc. 2014, 136,
11304; b) Y. Sasaki, Y. Horita, C. Zhong, M. Sawamura, H. Ito, Angew.
Chem. Int. Ed. 2011, 50, 2778; c) C. A. Brown, R. A. Coleman, J. Org.
Chem. 1979, 44, 2328.
(1) a) R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111, 1417; b)
D. Leonori, V. K. Aggarwal, Acc. Chem. Res. 2014, 47, 3174; c) N.
Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457; d) S. N. Mlynarski, A.
S. Karns, J. P. Morken, J. Am. Chem. Soc. 2012, 134, 16449; e) A.
Bonet, M. Odachowski, D. Leonori, S. Essafi, V. K. Aggarwal, Nat.
Chem. 2014, 6, 584; f) L. Li, S. Zhao, A. Joshi-Pangu, M. Diane, M. R.
Biscoe, J. Am. Chem. Soc. 2014, 136, 14027; g) J. C. Tellis, D. N.
Primer, G. A. Molander, Science 2014, 345, 433; h) L. J. Milo, Jr., J. H.
Lai, W. Wu, Y. Liu, H. Maw, Y. Li, Z. Jin, Y. Shu, S. E. Poplawski, Y.
Wu, D. G. Sanford, J. L. Sudmeier, W. W. Bachovchin, J. Med. Chem.
2011, 54, 4365.
(2) a) Boronic Acids: Preparation and Applications in Organic Synthesis
and Medicine (Ed.: D. G. Hall), Wiley-VCH, Weinheim, 2005; b) K.
Burgess, M. J. Ohlmeyer, Chem. Rev. 1991, 91, 1179; c) I. A. I.
Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig,
Chem. Rev. 2010, 110, 890.
(3) a) H. Y. Chen, S. Schlecht, T. C. Semple, J. F. Hartwig, Science 2000,
287, 1995; b) C.-T. Yang, Z.-Q. Zhang, Y.-C. Liu, L. Liu, Angew.
Chem., Int. Ed. 2011, 50, 3904; c)A. S. Dudnik, G. C. Fu, J. Am. Chem.
Soc. 2012, 134, 10693; d) T. C. Atack, R. M. Lecker, S. P. Cook, J. Am.
Chem. Soc. 2014, 136, 9521; e) T. C. Atack, S. P. Cook J. Am. Chem.
Soc., 2016, 138, 6139; f) J. He, Q. Shao, Q. Wu, J.-Q. Yu, J. Am. Chem.
Soc. 2017, 139, 3344; g) C. Li, J. Wang, L. M. Barton, S. Yu, M. Tian,
D. S. Peters, M. Kumar, A. W. Yu, K. A. Johnson, A. K. Chatterjee, M.
Yan, P. S. Baran, Science, 2017, 356, 6342.
(4) Recent reviews: a) M. Suginome, Chem. Rec. 2010, 10, 348; b) J. Yun,
Asian J. Org. Chem. 2013, 2, 1016; c) Y. Shimizu, M. Kanai,
Tetrahedron Lett. 2014, 55, 3727; d) K. Semba, T. Fujihara, J. Terao, Y.
Tsuji, Tetrahedron, 2015, 71, 2183; e) Y. Tsuji, T. Fujihara, Chem. Rec.
2016, 16, 2294; f) E. C. Neeve, S. J. Geier, I. A. Mkhalid, S. A.
Westcott, T. B. Marder, Chem. Rev. 2016, 116, 9091.
(9) a) Acetylene Chemistry: Chemistry, Biology and Material Science, F.
Diederich, P. J. Stang, R. R. Tykwinski, Eds., Wiley-VCH: Weinheim,
Germany, 2005; b) M. G. Finn, V. V. Fokin, Chem. Soc. Rev. 2010, 39,
1231; c) J. P. Brand, J. Waser, Chem. Soc. Rev. 2012, 41, 4165; d) R.
Chinchilla, C. Najera, Chem. Rev. 2014, 114, 1783; e) T. R. Wu, J. M.
Chong, J. Am. Chem. Soc., 2005, 127, 3244.
(10) For selected examples of C(sp)-C(sp3) cross-coupling: a) M. Eckhardt,
G. C. Fu, J. Am. Chem. Soc. 2003, 125, 13642; b) H. Bi, L. Zhao, Y.
Liang, C. Li, Angew. Chem., Int. Ed. 2009, 48, 792; c) S. Nicolai, C.
Piemontesi, J. Waser, Angew. Chem., Int. Ed. 2011, 50, 4689; d) O.
Vechorkin, A. Godinat, R. Scopelliti, X. Hu, Angew. Chem., Int. Ed.
2011, 50, 11981; e) Y. Ano, M. Tobisu, N. Chatani, J. Am. Chem. Soc.
2011, 133, 12984; f) J. He, M. Wasa, K. S. L. Chan, J.-Q. Yu, J. Am.
Chem. Soc. 2013, 135, 3387; g) F. Ye, X. Ma, Q. Xiao, H. Li, Y. Zhang,
J. Wang, J. Am. Chem. Soc. 2012, 134, 5742; h) J. Yi, X. Lu, Y.-Y. Sun,
B. Xiao, L. Liu, Angew. Chem., Int. Ed. 2013, 52, 12409; i) H. Fu, P.-X.
Shen, J. He, F. Zhang, S. Li, P. Wang, T. Liu, J.-Q. Yu, Angew. Chem.
Int. Ed. 2017, 56, 1873
(11) Y. Yang, I. B. Perry, G. Lu, P. Liu, S. L. Buchwald, Science 2016, 353,
144.
(12) a) A. Pathigoolla, R. P. Pola, K. M. Sureshan, Applied Catalysis A:
General, 2013, 453, 151; b) M. Cowart, R. Faghih, M. P. Curtis, G. A.
Gfesser, Y. L. Bennani, L. A. Black, L. Pan, K. C. Marsh, J. P. Sullivan,
T. A. Esbenshade, G. B. Fox, A. A. Hancock, J. Med. Chem. 2005, 48,
38; c) J. Chen, T. Xi, Z. Lu, Org. Lett., 2014, 16, 6452; d) V. Belting,
N. Krause, Org. Lett. 2006, 8, 4489; e) S. Li, S. Ma, Org. Lett., 2011,
13, 6046.
(13) a) M. K. Brown, T. L. May, C. A. Baxter, A. H. Hoveyda, Angew.
Chem. Int. Ed. 2007, 46, 1097; b) K. M. Logan, M. K. Brown, Angew.
Chem. Int. Ed. 2017, 56, 851; c) J. K. Park, D. T. McQuade, Angew.
Chem. Int. Ed. 2012, 51, 2717.
(5) a) R. T. Baker, P. Nguyen, T. B. Marder, S. A. Westcott, Angew. Chem.
Int. Ed. 1995, 34, 1336; b) Suginome, M.; Nakamura, H.; Ito, Y.
Angew. Chem., Int. Ed. 1997, 36, 2516; c) Y. Lee, A. H. Hoveyda, J.
Am. Chem. Soc. 2009, 131, 3160; d) L. T. Kliman, S. N. Mlynarski, J.
P. Morken, J. Am. Chem. Soc. 2009, 131, 13210; e) R. Corberán, N. W.
Mszar, A. H. Hoveyda, Angew. Chem. Int. Ed. 2011, 50, 7079; f) L.
Zhang, D. Peng, X. Leng, Z. Huang, Angew. Chem. Int. Ed. 2013, 125,
(14) A. Bonet, C. Pubill-Ulldemolins, C. Bo, H. Gulyás, E Fernández,
Angew. Chem. Int. Ed. 2011, 50, 7158.
(15) M. Suginome, M. Shirakura, A. Yamamoto, J. Am. Chem. Soc. 2006,
128, 14438.
(16) D. S. Laitar, E. Y. Tsui, J. P. Sadighi, Organometallics 2006, 25, 2405.
4
This article is protected by copyright. All rights reserved.

10.1002/asia.201701176
Chemistry - An Asian Journal
Entry for the Table of Contents (Please choose one layout)
Cross-Coupling
T.-J. Gong, S.-H.Yu, K. Li, W. Su, X. Lu,
B. Xiao,* and Yao Fu*
__________ Page – Page
Copper-Catalyzed Alkynylboration of
Alkenes with Diboron Reagents and
Bromoalkynes
A new and efficient method for the synthesis of homopropargylboronates by
copper-catalyzed alkynylboration of alkenes with diboron reagents and
bromoalkynes has been developed. The alkynylboration reaction features high
selectivity and efficiency, mild reaction conditions, wide substrate scope, and
functional-group compatibility, and is a highly attractive complement to existing
methods for the synthesis of homopropargylboronates. Both the boryl and alkynyl
groups are good potential functional groups, for the subsequent manipulations which
provide an efficient access to a variety of important molecule structures.
5
This article is protected by copyright. All rights reserved.