Copper-Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

Article abstract of DOI:10.1002/anie.201707323

A method for the copper-catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration of the alkene, followed by capture of the generated alkyl–copper intermediate with an acid chloride. The reactions operated with low catalyst loading and generally occurre within 15 min at room temperature for a range of activated alkenes. In the case of vinyl arenes, enantioselective borylacylation was possible.

Full text of DOI:10.1002/anie.201707323

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Accepted Article
Title: Cu-Catalyzed Borylacylation of Activated Alkenes with Acid
Chlorides
Authors: Michael Kevin Brown, Yuan Huang, and Kevin Smith
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201707323
Angew. Chem. 10.1002/ange.201707323
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10.1002/anie.201707323
Angewandte Chemie International Edition
COMMUNICATION
Cu-Catalyzed Borylacylation of Activated Alkenes with Acid
Chlorides
Yuan Huang, Kevin B. Smith and M. Kevin Brown*
Abstract: A method for Cu-catalyzed borylacylation of activated
alkenes is presented. The reaction involves the borylcupration of the
alkene followed by capture of the generated alkyl-Cu intermediate
with an acid chloride. The reactions operate with low catalyst
loading and generally occur within 15 min at room temperature for a
activated alkenes with widely available acid chlorides (Scheme
1C).19
A) Cross-Coupling with Acyl Electrophiles
Fe, Pd, Ni, Cu
catalyst
O
O
+
R2
[M]
range of activated alkenes.
In the case of vinyl arenes,
R1
X = Cl, SR, NR2
X
R1
R2
enantioselective borylacylation can be carried out.
[M] = SnR3,
ZnR, MgX, BR2
B) Arylboration of Alkenes by Pd/Cu-Cooperative Catalysis
Cross-coupling reactions of acyl electrophiles and
organometallic reagents represent a useful and well-established
strategy for the synthesis of ketones (Scheme 1A).1 This has
been shown to work with a variety of acyl electrophiles (e.g.,
acid chlorides,2 thioesters3 and activated amides4) as well as
organometallic reagents (e.g., Grignard,5 zinc,6 tin,7 and boron8).
More recent advances in this area have demonstrated that
coupling of acyl electrophiles and organohalides is possible in
the presence of a reducing agent.9
via:
Ar
Cu
Cu-catalyst
Pd-catalyst
R2
Bpin
R2
Bpin
R2
R1
R1
R1
ArBr, (Bpin)2
alkenyl arenes,
1,3 dienes, vinylsilanes,
strained alkenes
C) This Work
O
R1
R2
O
Cu-catalyst
(Bpin)2
(No Pd-catalyst
Required)
R1
R2
+
Ar/alkyl
pinB
Ar/alkyl
Cl
In recent years, Cu-catalyzed carboboration reactions of
alkenes have emerged as a useful strategy for chemical
synthesis because the C-B bond can be converted to other
groups with ease, thus allowing for carbofunctionalization. 10
• vinylarenes
• 1,3-dienes
• strained alkenes
• widely available
• easy to prepare
• New electrophile class for • Synthetically versatile products
,
13
Over the last several years, our group11 and others12 have
developed methods for the arylboration of alkenes by Cu/Pd-
cooperative catalysis (Scheme 1B). In these reactions, an alkyl-
Cu intermediate is generated by catalytic borylcupration of an
alkene followed by Pd-catalyzed cross-coupling. This strategy
has been shown to be effective for the functionalization of
alkenyl arenes, 1,3-dienes, vinylsilanes, and strained alkenes.
To extend the utility of these reactions, we desired to
develop a process in which acyl electrophiles could be employed
(Scheme 1C).14 This was viewed as a valuable strategy as the
products would represent versatile entities for chemical
synthesis and map onto molecules of biological interest
(Scheme 1D). 15 Though the direct formation of ketones is
unknown through a carboboration process, the Popp group
recently reported the boryl carboxylation of vinyl arenes to
generate carboxylic acids.16 While this is a significant advance,
in our view, direct synthesis of ketones from simple and widely
available precursors would be valuable to streamline synthesis.
In addition, it should be noted that Buchwald and coworkers
have developed Cu-catalyzed hydroacylation of alkenyl arenes
with anhydrides17 and more recently carboxylic acids.18 Herein,
a method is presented for the borylacylation of a variety of
carboboration
• Simple reaction setup (gram scale)
CHO
D) Representative Molecules
O
O
OMe
Me
OH
OH
HO
OBn
CO2H
OMe
antiviral agent
antihypertensive agent
Scheme 1. Relevant Precedent and Current Studies
Initial studies focused on utilizing thioester-derived
electrophiles in a Fukuyama-type cross coupling.3 Under all
conditions attempted, however, <2% of the desired
borylacylation product was observed (Scheme 2A). We then
turned our attention to the use of acid chlorides (e.g., 1).2 In this
case, the desired product 3 was observed, albeit in low yield.
Further analysis of the reaction through control experiments
revealed that the Pd-catalyst was not necessary. It appears that
the generated Csp3-Cu-complex 520 can undergo direct reaction
with an acid chloride according to the catalytic cycle shown in
,
Scheme 2B.21 22
[a]
Dr. Yuan Huang, Kevin B. Smith and Prof. M. Kevin Brown
Department of Chemistry
Indiana University
800 E. Kirkwood Ave. Bloomington, IN 47401
E-mail: brownmkb@indiana.edu
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201707323
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COMMUNICATION
A) Initial Findings
minimized the background formation of PhCO2t-Bu. This was
accomplished with the combination of Et2O and LiOt-Bu, in
which the base has minimal solubility. Other activated carbonyl
derivatives were evaluated (7-10) but did not allow for product
formation (Table 1, entries 2-5). As shown in Table 1, entries 6-
8, the reaction is largely specific to the use of SIMesCuCl.
Finally, it was observed that the yield of the reaction could be
improved if 2.0 equiv of base was used (Table 1, entries 12).
Furthermore, it was identified that the reaction could be run with
only 1 mol % SIMesCuCl and the reaction was complete in only
15 min (Table 1, entry 13). In addition, the reaction can be run
in air with nearly identical results to reaction carried out under
Cu-catalyst
Pd-catalyst
O
Ar
<2% product
+
+
SR1
R
NaOt-Bu, (Bpin)2
(Various Conditions)
5 mol % SIMesCuCl
with or without
Pd-XPhos-G3
O
O
Ph
Ph
Ph
Ph
Cl
NaOt-Bu, (Bpin)2
toluene, rt, 2 h
pinB
1
2
3
16% yield
with Pd-XPhos-G3
16% yield
without Pd-XPhos-G3
B) Proposed Catalytic Cycle for Cu-Catalyzed Borylacylation
inert atmosphere (Table 1, entry 14).
O
SIMesCuBpin
2
O
1 mol % SIMesCuCl
NaCl, t-BuOBpin
Ph
Ph
+
4
Ph
Ph
Cl
(Bpin)2, LiOt-Bu
Et2O, rt, 15 min
1
2
3
SIMesCu
pinB
Ph
pinB
72% yield
NaOt-Bu, (Bpin)2
(1.5 equiv)
(1.0 equiv)
SIMesCuCl
5
6
• Variation of Vinyl Arene
1
3
O
Scheme 2. Initial Findings and Proposed Catalytic Cycle
O
O
O
O
Ph
Ph
pinB
Ph
Table 1. Reaction Optimization
Cl
Me
11
12
13
pinB
pinB
O
55% yield
47% yield
74% yield
O
Cl
O
O
5 mol % SIMesCuCl
O
Ph
Ph
+
Ph
pinB
Ph
pinB
Ph
Cl
(Bpin)2 (1.5 equiv)
LiOt-Bu (1.5 equiv)
Et2O, rt, 3 h
Ph
Ph
1
2
3
CN
O
CO2Et
14
15
16
(1.5 equiv)
entry
(1.0 equiv)
pinB
pinB
yield (%)[a]
59% yield
O
89% yield
O
74% yield[a]
change from conditions
no change
1
88
<2
<2
<2
<2
56
25
6
H
H
7 instead of benzoyl chloride (1)
8 instead of benzoyl chloride (1)
9 instead of benzoyl chloride (1)
10 instead of benzoyl chloride (1)
IMesCuCl instead of SIMesCuCl
dpppCuCl instead of SIMesCuCl
dppbzCuCl instead of SIMesCuCl
NaOt-Bu instead of LiOt-Bu
2
Ph
Ph
NTs
3
H
4
17
67% yield
• Variation of Acid Chloride
OMe
18
pinB
pinB
5
Me
O
71% yield (1:1 dr)
6
7
O
O
F
O
8
Ph
Ph
Ph
O
R
9
56
13
54
98
98
96
THF instead of Et2O
10
11
12
13[b]
14[c]
19
20
21
toluene instead of Et2O
pinB
pinB
65% yield
O
pinB
67% yield[b]
2.0 equiv LiOt-Bu instead of 1.5 equiv LiOt-Bu
2.0 equiv LiOt-Bu instead of 1.5 equiv LiOt-Bu
2.0 equiv LiOt-Bu instead of 1.5 equiv LiOt-Bu
72% yield
O
O
R
Ph
Ph
24
Ph
O
Me Me
pinB
O
O
O
O
N
pinB
46% yield[b]
pinB
Ph
N
N
81% yield[b]
Ph
O
Ph
Ph
NBnBoc
R =
R =
Ph
S
Me (22)
Et (25) 46% yield[b]
i-Pr (26) 60% yield[b]
t-Bu (27) 77% yield[b]
7
8
9
10
[b]
OAc (23)
44% yield
PPh2
CuCl
PPh2
PPh2
MesN
NMes
CuBr
MesN
NMes
CuCl
PPh2
dpppCuCl
CuBr
SIMesCuCl
Scheme 3. Borylacylation of Vinyl Arenes and Acid Chlorides. Yield reported
dppbzCuCl
IMesCuCl
[a]
as the average of at least two experiments of isolated, purified product.
[b]
Reaction run for 30 min
2h.
5 mol % SIMesCuCl in toluene, 1.5 equiv LiOt-Bu,
[a]
[b]
Yield was determined by GC analysis with a calibrated internal standard.
Reaction with 1 mol % SIMesCuCl and run for 15 min. [c] Reaction with 1 mol
% SIMesCuCl and run for 15 min in air.
Under the optimized conditions, a range of vinyl arenes
and acid chlorides were investigated (Scheme 3). Electron rich
(product 12), electron poor (products 14 and 16), and sterically
From this result, the reaction was initially optimized to the
conditions shown in Table 1, entry 1. Key to the reaction
optimization was the identification of a solvent and base that
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10.1002/anie.201707323
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COMMUNICATION
O
demanding (products 13, 14, 15, and 16) vinyl arenes were
O
1 mol % SIMesCuCl
Ph
Ph
tolerated.
In addition, functional groups such as benzyl
(1)
+
Ph
Ph
Cl
(Bpin)2, LiOt-Bu
Et2O, rt, 1 h
chlorides (product 11), nitriles (product 14), aryl chlorides
(product 16), ketones (product 18), and esters (product 15) did
not inhibit product formation to any significant degree. At this
time, attempted borylacylation of 1,2-disubstituted alkenyl
arenes only resulted in recovered starting material (not shown).
With respect to the acid chloride component, in addition to aroyl
chlorides of various steric and electronic properties (products
19-21), alkyl acid chlorides could also be used (products 22-27).
pinB
1.37g
82% yield
3
1
2
(1.5 equiv)
5.0 mmol
(1.0 equiv)
Br
O
Br
O
2 mol % SIMesCuCl
Cl
(2)
+
(Bpin)2, LiOt-Bu
Et2O, rt, 2 h
Cl
Cl
pinB
41
(1.5 equiv)
42
43
10.0 mmol
(1.0 equiv)
3.30g
74% yield
A) Reactions of 1,3-Dienes
Ph
Ph
+
Ph
5 mol %
SIMesCuCl
O
t-Bu
The borylacylation reaction can also be carried out on
gram scale with an operationally simple protocol. The reactions
illustrated in eqns (1) and (2) exemplify this point.
O
+
t-Bu
pinB
O
t-Bu
Cl
(Bpin)2, LiOt-Bu
Et2O, rt, 2 h
28
29
30
31
(1.5 equiv) (1.0 equiv)
Bpin
78% yield[a]
2.5:1 (1,2 (30):1,4 (31))
O
O
2 mol % Pd2(dba)3
4 mol % RuPhos
Ph
Ph
O
Ph
Ph
O
as
above
as
above
Ph
pinB
Ph
Me
Me
NaOt-Bu
toluene:H2O (10:1)
80 ºC, 24 h
MeO
Ar
Me
Ph
Me
3
44
32
33
78% yield
>20:1 (1,2:1,4)
34
35
55% yield
>20:1 (1,2:1,4)
Ar = 2-furyl
pinB
pinB
MeO
Br
62% yield
O
B) Reactions of Strained Bicyclic Alkenes
O
O
Ph
pinB
O
1 mol % SIMesCuCl
5 mol % Grubbs I
Ph
pinB
Ph
pinB
+
Ph
Cl
ethylene (1 atm)
CH2Cl2, rt, 24 h
(Bpin)2, LiOt-Bu
Et2O, rt, 15 min
1
36
37
37
45
53% yield
(1.5 equiv)
(1.0 equiv)
74% yield, >20:1 dr
O
O
Ph
pinB
O
O
O
O
O
O
O
OBz
OBz
Ph
pinB
1) NaBO3•4H2O
THF:H2O (1:1), rt, 1 h
Ph
pinB
O
Me OH
Ph
Ph
38
78% yield, >20:1 dr[b]
39
40
2) i) LiH, toluene,
-40 ºC, 15 min
ii)TiCl4, -78 ºC, 45 min
iii) MeMgBr,
70% yield, >20:1 dr
67% yield, >20:1 dr
46
pinB
Br
HO
[a]
9
Scheme 4. Borylacylation of Various Activated Alkenes.
Yield determined
47% yield, >20:1 dr
(2 steps)
by 1H NMR analysis with an internal standard of the combined mixture of 1,2-
and 1,4-borylacylation products. [b] Reaction run for 2 h.
-78 ºC to rt, 30 min
1) NaBO3•4H2O
THF:H2O (1:1), rt, 1 h
Br
OH
O
A notable aspect of this study is that the borylacylation
reaction can be extended to other classes of activated alkenes
(Scheme 4). Reaction of 1-phenylbutadiene (29) under the
standard conditions resulted in the formation of a mixture of 1,2-
(30) and 1,4-borylacylation products (31).11d,e The formation of
the 1,4-borylacylation product could be suppressed provided
that an additional substituent is present, as in diene 32. 2,3-
dimethylbutadiene could also be used, and resulted in exclusive
formation of the 1,2-borylacylation product 35, which bears a
quaternary carbon. Finally, bicyclic strained alkenes could also
be used in this reaction. In all cases, the products (37-40) were
generated as a single diastereomer in good yield.
2) i) LiH, toluene,
-40 ºC, 15 min
ii)TiCl4, -78 ºC, 45 min
iii) LiBH4,
Cl
Cl
HO
pinB
47
43
77% yield, >20:1 dr
(2 steps)
-78 ºC to rt, 30 min
20 mol % CuI
30 mol %
MeHN
OH
O
NHMe
Cs2CO3, MeCN
60 ºC, 12 h
Cl
48
69% yield
Scheme 5. Transformations of Borylacylation Products
The products of the borylacylation reaction represent
useful intermediates for chemical synthesis (Scheme 5). The
primary alkyl-Bpin 3 was also subjected to cross-coupling
conditions to provide 44 in 62% yield.23 Due to the ring strain of
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10.1002/anie.201707323
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COMMUNICATION
bicyclic alkene 37, ring-opening cross-metathesis with ethylene
allowed for the formation of 45. After oxidation of the Bpin unit
of 9 to an alcohol, highly diastereoselective addition of a methyl
Grignard could be carried out to generate 46. 24 Likewise,
diastereoselective reduction of the oxidized product of 43 could
be carried out to provide 47. This intermediate (47) could also
be cyclized under Cu-catalysis to provide chromane derivative
48.25
Finally, enantioselective borylacylation of vinyl arenes was
briefly investigated (Scheme 6). After evaluation of a series of
catalysts, Cu-complex 49 allowed for formation of (R)-3 in 85:15
er. Additional efforts led to the determination that sterically
demanding vinyl arenes allowed for formation of the desired
product with higher yields and enantioselectivity (products (R)-
13 and (R)-17). Borylacylation product (R)-13 (which was
prepared on 1.0 mmol scale) could be recrystallized to afford the
compound in 99:1 er and ultimately allowed for absolute
structure determination by X-ray crystallography. The Bpin unit
of (R)-13 could also be oxidized to generate the corresponding
alcohol without loss in enantiopurity.26 Finally, it should be noted
that chiral Cu-complex 49 was easily prepared in two steps from
commercially available materials.
Keywords: Boron • Alkenes • Catalysis • Acid Chloride • Copper
1 For reviews, see: (a) R. K. Dieter, Tetrahedron 1999, 55, 4177. (b) T.
Fukuyama, H. Tokuyama, H. Aldrichimica Acta 2004, 37, 87. (c) L. J.
Gooßen, N. Rodríguez, K. Gooßen, Angew. Chem. Int. Ed. 2008, 47,
3100.
2 D. Milstein, J. K. Stille, J. Am. Chem. Soc. 1978, 78, 3636.
3
H. Tokuyama, S. Yokoshima, T. Yamashita, T. Fukuyama,
Tetrahedron Lett. 1998, 39, 3189
4 For selected recent examples, see: (a) G. Meng, M. Szostak, Org.
Lett. 2015, 17, 4364 . (b) N. A. Weires, E. L. Baker, N. K. Garg, Nat.
Chem. 2015, 8, 75 .
5
For example, see: B. Scheiper, M. Bonnekessel, H. Krause, A.
Fürstner, J. Org. Chem. 2004, 69, 3943.
6 For example, see: ref (3)
7 For example, see: ref (2)
8 For example, see: L. S. Liebeskind, J. Srogl, J. Am. Chem. Soc. 2000,
122, 11260.
9 (a) A. C. Wotal, D. J. Weix, Org. Lett. 2012, 14, 1476. (b) A. H.
Cherney, N. T. Kadunce, S. E. Reisman, J. Am. Chem. Soc. 2013, 135,
7442.
10 For reviews, see: (a) Y. Shimizu, M. Kanai, Tetrahedron Lett. 2014,
55, 3727. (b) K. Semba, T. Fujihara, J. Terao, Y. Tsuji, Tetrahedron
2015, 71, 2183. (c) F. Lazreg, F. Nahra, C. S. J. Cazin, Coord. Chem.
Rev. 2015, 293-294, 48. (d) E. C. Neeve, S. J. Geier, I. A. I. Mkhalid,
S. A. Westcott, T. B. Marder, Chem. Rev. 2016, 116, 9091.
11 (a) K. B. Smith, K. M. Logan, W. You, M. K. Brown, Chem. Eur. J.
2014, 20, 12032. (b) K. M. Logan, K. B. Smith, M. K. Brown, Angew.
Chem. 2015, 127, 5317. (c) K. M. Logan, M. K. Brown, Angew.
Chem. 2016, 129, 869. (d) K. B. Smith, M. K. Brown, J. Am. Chem.
Soc. 2017, 139, 7721. (e) S. R. Sardini, M. K. Brown, J. Am. Chem.
Soc. 2017, 139, 9823.
10 mol %
Me
t-Bu
Me
N
N
O
t-Bu
CuBr
O
Ph
49
Ph
+
Ph
Ph
Cl
(Bpin)2, LiOt-Bu
(R)-3
1
2
Et2O:hexanes (1:1)
rt, 2 h
pinB
(1.5 equiv)
O
(1.0 equiv)
48% yield
85:15 er
12 For a closely related study that was reported contemporaneously with
our initial publication, see: K. Semba, Y. Nakao, J. Am. Chem. Soc.
2014, 136, 7567.
O
13 (a) T. Jia, P. Cao, B. Wang, Y. Lou, X. Yin, M. Wang, J. Liao, J.
Am. Chem. Soc. 2015, 137, 13760. (b) B. Chen, P. Cao, X. Yin, Y.
Liao, L. Jiang, J. Ye, M. Wang, J. Liao, ACS Catal. 2017, 7, 2425 .
Ph
pinB
Ph
pinB
NTs
Me
14
(R)-13
(R)-17
For representative examples of Cu-catalyzed carboboration of
X-ray of (R)-13
(after recrystalization
to >99:1 er)
78% yield
88:12 er
(1 mmol scale)
alkenes with aldehydes, ketones and imines, see: (a) F. Meng, H. Jang,
B. Jung, A. H. Hoveyda, Angew. Chem. Int. Ed. 2013, 52, 5046. (b) F.
Meng, F. Haeffner, A. H. Hoveyda, J. Am. Chem. Soc. 2014, 136,
11304–11307. (c) K. Yeung, R. E. Ruscoe, J. Rae, A. P. Pulis, D. J.
Procter, Angew. Chem. 2016, 128, 12091. (d) L. Jiang, P. Cao, M.
Wang, B. Chen, B. Wang, J. Liao, Angew. Chem. Int. Ed. 2016, 55,
13854. (e) J. C. Green, M. V. Joannou, S. A. Murray, J. M. Zanghi, S.
J. Meek, ACS Catal. 2017, 4441.
66% yield
88:12 er
Scheme 6. Enantioselective Borylacylation of Vinylarenes
In summary, a method for the borylacylation of activated
alkenes with acid chlorides is presented. The method was
shown to include vinyl arenes, 1,3-dienes, and strained bicyclic
alkenes in addition to acid chlorides of varying steric and
electronic properties. Due to the short reaction times and use of
readily available starting materials the method is straightforward
and practical. Future efforts will focus on expanding the scope
of alkenes that can be utilized.
15 (a) P. C. Astles, T. J. Brown, N. V. Harris, M. F. Harper, Eur. J.
Med. Chem 1997, 32, 515. (b) J.-Q. Yu, W. Hang, W.-J. Duan, X.
Wang, D.-J. Wang, X.-M. Qin, Phytochemistry Lett. 2014, 10, 230.
16 T. W. Butcher, E. J. McClain, T. G. Hamilton, T. M. Perrone, K. M.
Kroner, G. C. Donohoe, N. G. Akhmedov, J. L. Petersen, B. V. Popp,
Org. Lett. 2016, 18, 6428.
17 J. S. Bandar, E. Ascic, S. L. Buchwald, J. Am. Chem. Soc. 2016, 138,
5821.
18 Y. Zhou, J. S. Bandar, S. L. Buchwald, J. Am. Chem. Soc. 2017, 139,
8126.
Acknowledgements
19 For a Pd-catalyzed borylacylation of allenes, see: F.-Y. Yang, M.
Shanmugasundaram, S.-Y. Chuang, P.-J. Ku, M.-Y. Wu, C.-H. Cheng,
J. Am. Chem. Soc. 2003, 125, 12576.
We thank Indiana University, the National Institutes of Health
(1R01GM114443), and the ACS-PRF (54422-DNI) for generous
financial support. This project was partially funded by the Vice
Provost for Research through the Research Equipment Fund.
20 D. S. Laitar, E. Y. Tsui, J. P. Sadighi, Organometallics 2006, 25,
2405.
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COMMUNICATION
21 Addition of cuprates to acid chlorides is known. (a) For a seminal
report, see: G. H. Posner, C. E. Whitten, J. Am. Chem. Soc. 1972, 94,
5106. (b) For a review, see: ref (1a).
In situ generation of Cu-complex 5 and reaction with benzoyl
chloride is rapid (<15 min) and produced 3 in 62% yield. See the
23 C.-T. Yang, Z.-Q. Zhang, H. Tajuddin, C.-C. Wu, J. Liang, J.-H. Liu,
Y. Fu, M. Czyzewska, P. G. Steel, T. B. Marder, et al., Angew. Chem.
Int. Ed. 2011, 51, 528.
22
24 G. Bartoli, M. C. Bellucci, M. Bosco, Chem. Eur. J. 1998, 4, 2154.
25 (a) R. A. Altman, A. Shafir, A. Choi, P. A. Lichtor, S. L. Buchwald,
J. Org. Chem. 2008, 73, 284–286. (b) W. Yang, Y. Liu, S. Zhang, Q.
Cai, Angew. Chem. 2015, 127, 8929–8932.
Supporting Information for details.
26 See the Supporting Information for details.
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10.1002/anie.201707323
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Yuan Huang, Kevin B. Smith and M.
Kevin Brown*
Page No. – Page No.
Cu-Catalyzed Borylacylation of
Activated Alkenes with Acid
Chlorides
A method for Cu-catalyzed borylacylation of activated alkenes is presented. The
reaction involves the borylcupration of the alkene followed by capture of the
generated alkyl-Cu intermediate with an acid chloride. The reactions operate with
low catalyst loading and generally occur within 15 min at room temperature for a
range of activated alkenes.
borylacylation can be carried out.
In the case of vinyl arenes, enantioselective
Abstract Image:
O
R1
O
Cu-catalyst
(Bpin)2
R1
R2
+
Ar/alkyl
pinB
Ar/alkyl
Cl
R2
• vinylarenes
• widely available
• easy to prepare
• 1,3-dienes
• strained alkenes
This article is protected by copyright. All rights reserved.