Nickel-Catalyzed Ligand-Free Hiyama Coupling of Aryl Bromides and Vinyltrimethoxysilane

Article abstract of DOI:10.1055/a-1379-1584

We herein disclose the first Ni-catalyzed Hiyama coupling of aryl halides with vinylsilanes. This protocol uses cheap, nontoxic, and stable vinyltrimethoxysilane as the vinyl donor, proceeds under mild and ligand-free conditions, furnishing a diverse variety of styrene derivatives in high yields with excellent functional group compatibility.

Full text of DOI:10.1055/a-1379-1584

SYNLETT
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart
2021, 32, A–E
cluster
A
Modern Nickel-Catalyzed Reactions
S. Wei et al.
Cluster
Synlett
Nickel-Catalyzed Ligand-Free Hiyama Coupling of Aryl Bromides
and Vinyltrimethoxysilane
Shichao Weia,b
Yongjun Mao*a
Shi-Liang Shi*a,b
NiCl2(glyme) (10 mol%)
TBAT (2.5 eq.)
Br
R
Het
Si(OMe)3
2.0 eq.
Het
R
+
DMA (0.2 M)
rt or 50 °C, 12 h
>26 examples
up to 90% yield
0
0
0
0-0
0
0
2
-0
6
2
4
-
6
8
2
4
R = ester, ketone, aldehyde, cyanide, amide, sulfonyl, sulfonamide, morpholinyl, etc.
a College of Chemistry and Chemical Engineering, Shanghai
University of Engineering Science, Shanghai 201620,
P. R. of China
yongjun.mao@hotmail.com
b State Key Laboratory of Organometallic Chemistry, Center
for Excellence in Molecular Synthesis, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 345
Lingling Road, Shanghai 200032, P. R. of China
shiliangshi@sioc.ac.cn
Published as part of the Cluster
Modern Nickel-Catalyzed Reactions
Corresponding Authors
Received: 30.11.2020
a) Pd-catalyzed vinylation of aryl halides
Accepted after revision: 31.01.2021
Published online: 31.01.2021
DOI: 10.1055/a-1379-1584; Art ID: st-2020-k0612-c
X
Pd/L (cat.)
R
+
R
M
X = Cl, Br, I, OTf, or OTs
M = Mg, Al, B, Si, or Sn
Abstract We herein disclose the first Ni-catalyzed Hiyama coupling
of aryl halides with vinylsilanes. This protocol uses cheap, nontoxic, and
stable vinyltrimethoxysilane as the vinyl donor, proceeds under mild
and ligand-free conditions, furnishing a diverse variety of styrene deriv-
atives in high yields with excellent functional group compatibility.
b) Ni-catalyzed coupling of aryl magnesium and vinyl chloride
MgBr
NiCl2(dpe) (cat.)
+
Cl
R
R
Kumada et al.
c) Ni-catalyzed vinylation of aryl halides using vinylzinc
Ni(acac)2
Keywords nickel catalysis, vinylation, cross-coupling, Hiyama cou-
pling, ligand-free conditions, vinylsilane, aryl halide
Xantphos
(cat.)
X
R
R
+
ZnBr MgBrCl
Yamakawa et al.
d) Ni-catalyzed reductive coupling of aryl halides and vinyl bromides
Styrene derivatives represent one of the most important
structural units in organic chemistry. Moreover, they serve
as versatile synthetic intermediates in various organic
transformations, such as olefin metathesis,1 Heck reaction,2
hydrofunctionalization,3 and epoxidation.4 Besides, they are
widely used as monomers for polymer synthesis.5 The tra-
ditional synthetic methods of styrenes include dehydration
of alcohols or Hoffman elimination,6 carbonyl olefination,7
and semireduction of terminal alkynes.8 However, these
methods, to some extent, are limited by the accessibility of
the starting materials, harsh reaction conditions, or the tol-
erance of functional groups.
In order to address the above-mentioned issues, numer-
ous transition-metal-catalyzed cross-coupling reactions us-
ing readily available aryl halides have been developed to ac-
cess styrenes in the past several decades.9 For example, Pd-
catalyzed vinylation of aryl halides using magnesium-,10
lithium-,11 aluminium-,12 boron-,13 silicon-,14 and tin-
based15 vinyl donors has been reported and widely applied
to the synthesis of vinyl arenes (Scheme 1a). However,
these methods generally suffer from the use of noble metal,
expensive and sensitive ligand, and in some cases using
toxic or unstable organometallic reagents. Therefore, a mild
earth-abundant metal-catalyzed vinylation of aryl halides
Ni(COD)2
R'
dtbbp
X
R'
(cat.)
R
+
Zn
+
R
Br
Gong et al.
e) Ni-catalyzed vinylation of aryl bromides using vinylsilane (this work)
NiCl2(glyme)
(10 mol%)
base
Br
R
R
+
Si(OMe)3
ligand-free
Scheme 1 Pd- or Ni-catalyzed cross-couplings to form styrenes
using stable vinyl donors is highly desirable and yet re-
mains underdeveloped.
As the first-row transition metal in the same group as
palladium, nickel has attracted much attention from the
chemical community due to its earth-abundant, cost-effec-
tive characteristics, and numerous nickel-catalyzed reac-
tions have been developed.16 In 1972, Kumada and co-
workers described a pioneering work on Ni-catalyzed
cross-coupling reaction of aryl Grignard reagent with vinyl
chloride (Scheme 1b).17 In 2009, Yamakawa and co-workers
reported a Ni-catalyzed coupling of vinyl zinc reagents and
aryl halides (Scheme 1c).18 In 2016, Gong and co-workers
reported an elegant Ni-catalyzed reductive coupling of aryl
© 2021. Thieme. All rights reserved. Synlett 2021, 32, A–E
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
S. Wei et al.
Cluster
Synlett
halides and vinyl bromides using Zn as the reducing agent
(Scheme 1d).19 We noted that vinylsilanes have the advan-
tages of easy accessibility, low toxicity, and high stability,
thus serve as excellent vinyl donors. Although Pd-catalyzed
Hiyama coupling of aryl halides with silicon reagents is
well-developed,14,20 the Ni-catalyzed Hiyama cross-cou-
pling reaction is relatively underexplored.21,22 As far as we
know there is no report on the Ni-catalyzed cross-coupling
reaction of vinyl silicon reagents with aryl halides. As a part
of our continuous interests in nickel catalysis,23 we herein
report a ligand-free Ni-catalyzed Hiyama coupling of aryl
halides with vinylsilanes to prepare styrenes (Scheme 1e).
We started our studies by using commercially available
vinyltrimethoxysilane (2) and aryl bromide 1a as model
substrates and base and 18-crown-6 as activators in the
presence of stable divalent nickel catalysts to optimize the
reaction conditions (Table 1). We found that inorganic bases
such as KOMe, NaOMe, and KOt-Bu were effective for the vi-
nylation reaction at ambient temperature (35 °C), affording
product 3a in good yield (ca. 80%, entries 1–4), but KF led to
no conversion (entry 5). The use of cyclohexane and di-
chloromethane as solvent resulted in low or no conversions,
but more polar solvents, such as DMF, DMA, dioxane, and
THF produced 3a in high yields (entries 1, 6–10). Among
these solvents, DMF is the best choice. The use of different
divalent nickel sources gave similar reaction outcomes (en-
tries 11 and 12). Increasing the amount of vinylsilane and
base to 2.3 equivalents could improve the yield to 87% (en-
try 13, 84% isolated yield). The control experiment con-
firmed that 18-crown-6 is critical to promote the reaction
(entry 14).
Under the reaction conditions shown in Table 1, entry
13, we examined the preliminary substrate scope of this re-
action. As shown in Scheme 2, we found that electronically
neutral aryl bromides could furnish the corresponding vinyl
arene products in 63–84% yield (3a–e). Unfortunately, an
electron-rich substrate (3f) gave no conversion under ambi-
ent temperature or delivered a trace amount of product at
elevated temperature (50 °C).
Br
NiCl2(glyme) (10 mol%)
R
R
Si(OMe)3
KOMe (2.3 eq.)
18-crown-6 (2.3 eq.)
DMF (0.2 M), rt, 12 h
1 (0.2 mmol)
2 (2.3 eq.)
3
MeO
3b, 78%
3c, 71%
3f, 0%
3a, 84%
tBu
Me2N
3d, 66%
3e, 63%
Br
3g, 0%
OMe
MeOOC
MeOOC
MeOOC
Table 1 Reaction Optimization
NiCl2(glyme) (10 mol%)
+
KOMe or KOtBu (2.3 eq.)
18-crown-6 (2.3 eq.)
DMF (0.2 M), rt, 12 h
catalyst (10 mol%)
base (2.0 eq.)
Si(OMe)3
Br
3g', 60% (using KOMe)
Si(OMe)3
+
2 (2.3 eq.)
65% (using KOtBu)
18-crown-6 (2.0 eq.)
solvent (0.2 M)
rt, 12 h
MeO
MeO
Scheme 2 Preliminary substrate scope
1a (0.2 mmol)
2 (2.0 eq.)
3a
Entry
Catalyst
Base
KOMe
Solvent
Yield (%)a
Interestingly, electron-deficient substrates underwent
carbon–oxygen (C–O) formation to give an aryl methyl
ether (3g′) but not the desired vinylation product (3g). The
use of KOt-Bu as the base gave aryl methyl ether (3g′) and
suggests that the methoxy group in the product results
from vinyltrimethoxysilane but not from the base KOMe.24
To address this chemoselectivity issue, we felt the use of
a more selective silane activator could be required. We not-
1
2
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiBr2(glyme)
NiCl2
THF
THF
THF
THF
THF
80
74
54
33
0
NaOMe
KOt-Bu
KOt-Bu
KF
3
4
5
6
KOMe
KOMe
KOMe
KOMe
KOMe
KOMe
KOMe
KOMe
KOMe
dioxane
DMF
75
83
76
0
ed
that
tetrabutylammoniumtriphenyldifluorosilicate
7
(TBAT), a commercially available, anhydrous, nonhygro-
scopic, crystalline solid, was first introduced as a fluoride
source by DeShong and co-workers.25 TBAT was found less
basic than tetrabutylammonium fluoride (TBAF) but could
more efficiently activate silicon–carbon bonds to generate
in situ carbanions to couple with electrophiles.25,26 Intrigu-
ingly, TBAT itself served as a phenylating agent in Pd-cata-
lyzed cross-coupling reactions of aryl halides.26b However,
in a Ni-catalyzed asymmetric Hiyama coupling of -bromo
esters, TBAT worked as an activator for aryltrimethoxysi-
lane but not as a phenylating agent.21d
8
DMA
DCM
hexane
DMF
9
10
11
12
13b
14c
37
80
82
87 (84)
<2
DMF
NiCl2(glyme)
NiCl2(glyme)
DMF
DMF
a Determined by GC using crude samples, the isolated yield is shown in pa-
renthesis.
b Using 2.3 equiv of 2, KOMe, and 18-crown-6.
c Without 18-crown-6.
© 2021. Thieme. All rights reserved. Synlett 2021, 32, A–E

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We next optimized the reaction conditions using TBAT
as a nucleophilic activator for the Hiyama coupling of vinyl-
Notably, electron-deficient aryl bromides that did not work
under our initial conditions (Table 1, entry 11) served as
suitable substrates, affording the corresponding vinylation
products in high yields (3h–u). The potential biaryl byprod-
uct (TBAT as a phenylating reagent) and the aryl methyl
ethers (methoxy migration from silane) were not observed
under these mild reaction conditions. A wide variety of
functional groups, including esters, aldehydes, ketones, ni-
triles, sulfone, amides, sulfonamides, ethers, and mor-
pholinyl groups, were compatible (3a–y). For electron-rich
aryl bromides (3w–y) and heteroaromatic substrates (3z–
4e), the reactions proceeded smoothly when heating the
reaction mixtures to 50 °C. Various heterocycles, such as
benzothiophene, benzofuran, isoquinoline, and quinoxal-
ine, were all competent substrates, delivering vinyl het-
eroarenes in good to high yields (3z–4d). However, an at-
tempt to synthesize -substituted styrenes using (E)-styryl-
triethoxysilane instead of 2 failed (4e).
silane
2 and aryl bromide 1b in the presence of
NiCl2(glyme) catalyst at ambient temperature (35 °C). To
our delight, the new conditions afforded the vinylation
product 3b in 68% yield without observing the correspond-
ing phenylation byproduct (TBAT as a phenylating reagent)
(Table 2, entry 5). Remarkably, other fluoride sources such
as TBAF, KF, NaF, and CsF resulted in no conversions (entries
1–4). A solvent screening suggested DMA is the best sol-
vent, furnishing 3b in 83% yield (entries 5–9). Other nickel
sources, such as NiBr2(glyme) and NiCl2, decreased the yield
slightly (entries 10 and 11). However, when increasing the
amount of vinyl donor (2.0 equiv) and TBAT (2.5 equiv), the
yield could be improved to 87% (83% isolated yield, entry
12). Finally, the reaction was found applicable to aryl iodide
and aryl triflate affording 3b good yields, although aryl
chloride and aryl tosylate were unsuitable substrates (en-
tries 13–16).
Br
NiCl2(glyme) (10 mol%)
TBAT (2.5 eq.)
Si(OMe)3
2 (2 eq.)
Het
R
R
Het
3, 4
Table 2 Reaction Optimization
DMA (0.2 M)
rt ,12 h
1 (0.2 mmol)
Br
catalyst (10 mol%)
Si(OMe)3
+
EtO
TBAT (2.0 eq.)
solvent (0.2 M), rt, 12 h
1b (0.2 mmol)
2 (1.5 eq.)
3b
MeO
O
3b, 83%
3a, 82%
3c, 78%
3k, 65%
3h, 70%
Entry
X
Catalyst
Base
Solvent
Yield (%)a
1
2
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiBr2(glyme)
NiCl2
KF
dioxane
dioxane
dioxane
dioxane
dioxane
THF
0
0
MeO
MeO
H
Me
NaF
O
O
O
O
3i, 83%
3j, 79%
3n, 84%
3l, 82%
3
CsF
0
4
TBAF
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
TBAT
0
Et
Ph
5
68
75
20
74
83
67
73
87 (83)
0
NC
NC
O
O
O
S
6
3m, 66%
3o, 81%
3p, 85%
7
DCM
Me
8
DMF
O
O
N
S
Me
S
O
9
DMA
Me
Me
Me
O
O
O
10
11
12b
13b
14b
15b
16b
DMA
3q, 75%
3r, 85%
3s, 74%
3t, 90%
DMA
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
NiCl2(glyme)
DMA
O
S
N
O
DMA
nBu
Me2N
O
O
O
I
DMA
70
67
11
3w, 65%a
3x, 63%a
3u, 81%
3v, 56%
OTf
OTs
DMA
S
DMA
N
O
a Determined by GC analysis. The isolated yield is shown in parenthesis.
O
b Using 2.0 equiv of 2 and 2.5 equiv of TBAT.
3y, 84%a
3z, 45%a
4a, 69%a
4b, 70%a
N
N
Ph
With the optimized reaction conditions in hand, we
next surveyed the generality of this novel Ni-catalyzed pro-
tocol (Scheme 3). We found that this reaction is not sensi-
tive to steric hindrance; bulky substrates work well (3c,s).
Ph
N
using (EtO)3Si
4e, 0%a,b
4c, 70%a
4d, 64%a
Scheme 3 Substrate scope. a Reaction performed at 50 °C. b Using (E)-
styryltriethoxysilane instead of 2.
© 2021. Thieme. All rights reserved. Synlett 2021, 32, A–E

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Finally, we successfully performed two examples of
gram-scale reactions. Similar high yields of products were
obtained, which highlighting the robustness and practicali-
ty of our catalytic method (Scheme 4).
(8) Chinchilla, R.; Najera, C. Chem. Rev. 2014, 114, 1783.
(9) Denmark, S.; Butler, C. R. Chem. Commun. 2009, 20.
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271.
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Gotov, B. Synlett 2003, 1783.
NiCl2(glyme)
(10 mol%)
Br
TBAT (2.5 eq.)
+
Si(OMe)3
DMA (0.4 M)
rt, 12 h
(13) (a) Kerins, F.; O’Shea, D. F. J. Org. Chem. 2002, 67, 4968.
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Han, J.; Liu, J.; Li, Y.; Zhang, F.; Yu, H.-Z.; Hu, S.; Wang, X. Chem.
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Lichtenfeld, C.; Gilmour, R. Angew. Chem. Int. Ed. 2019, 58,
18619.
10 mmol
2.0 eq.
3b, 78% (1.20 g)
NiCl2(glyme)
(10 mol%)
KOMe (2.3 eq.)
Br
Si(OMe)3
+
18-crown-6 (2.3 eq.)
DMF (0.2 M)
rt, 12 h
MeO
3a, 84% (1.55 g)
MeO
10 mmol
2.3 eq.
Scheme 4 Gram-scale reactions
In conclusion, we have developed a Ni-catalyzed Hiyama
coupling reaction of aryl bromides and vinylsilanes for the
first time.27 The key to the success of the transformation is
the use of TBAT as a silane-activating reagent. This protocol
uses inexpensive nickel catalyst under ligand-free condi-
tions, employs readily available and stable substrates, dis-
plays both high tolerance of functional groups and scale-up
capacity.
(15) (a) William, J.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1986, 108,
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(c) Littke, A. F.; Schwarz, L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124,
6343.
Funding Information
(16) For selected reviews on Ni-catalyzed coupling reactions, see:
(a) Tasker, S. Z.; Standley, E. A.; Jamison, T. F. Nature 2014, 509,
299. (b) Moragas, T.; Correa, A.; Martin, R. Chem. Eur. J. 2014, 20,
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43, 8081. (d) Su, B.; Cao, Z. C.; Shi, Z.-J. Acc. Chem. Res. 2015, 48,
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(f) Weix, D. J. Acc. Chem. Res. 2015, 48, 1767. (g) Gu, J.; Wang, X.;
Xue, W.; Gong, H. Org. Chem. Front. 2015, 2, 1411. (h) Henrion,
M.; Ritleng, V.; Chetcuti, M. J. ACS Catal. 2015, 5, 1283. (i) Choi,
J.; Fu, G. C. Science 2017, 356, eaaf7230. (j) Modern Organonickel
Chemistry; Tamaru, Y., Ed.; Wiley-VCH: Weinheim, 2006.
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1972, 94, 4374.
(18) Yamamoto, T.; Yamakawa, T. J. Org. Chem. 2009, 74, 3603.
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55, 15544.
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Nikpassan, M.; Hosseinian, A. RSC Adv. 2019, 9, 3185.
(b) Organosilicon Chemistry; Hiyama, T.; Oestreich, M., Ed.;
Wiley-VCH: Weinheim, 2019. (c) Komiyama, T.; Minami, Y.;
Hiyama, T. ACS Catal. 2017, 7, 631.
(21) For selected examples on coupling reaction of aryl silicon com-
pounds and alkyl halides, see: (a) Lee, J.-Y.; Fu, G. C. J. Am. Chem.
Soc. 2003, 125, 5616. (b) Powell, D. A.; Fu, G. C. J. Am. Chem. Soc.
2004, 126, 7788. (c) Lee, J.-Y.; Fu, G. C. J. Am. Chem. Soc. 2003,
125, 5616. (d) Dai, X.; Strotman, N. A.; Fu, G. C. J. Am. Chem. Soc.
2008, 130, 3302.
(22) For selected examples on coupling reaction of aryl silicon com-
pounds and aryl halides, see: (a) Tang, S.; Takeda, M.; Nakao, Y.;
Hiyamaz, T. Chem. Commun. 2011, 47, 307. (b) Tang, S.; Li, S. H.;
Nakao, Y.; Hiyamaz, T. Asian J. Org. Chem. 2013, 2, 416.
This work was financially supported by the National Natural Science
Foundation of China (NSF, Grant No. 91856111, 21871288, 21690074,
21821002), the Strategic Priority Research Program of the Chinese
Academy of Sciences (Grant No. XDB20000000).
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/a-1379-1584. Su
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References and Notes
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© 2021. Thieme. All rights reserved. Synlett 2021, 32, A–E

E
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diluted with EtOAc and washed with water. The organic phase
was dried over Na2SO4, filtered, and concentrated, and the
residue was purified by column chromatography on silica gel to
give the product.
2-Methoxy-6-vinylnaphthalene (3a)
Using general procedure 1: white solid, 31.0 mg, yield: 84%. 1H
NMR (400 MHz, CDCl3):  = 7.78–7.66 (m, 3 H), 7.62 (dd, J = 8.7,
1.7 Hz, 1 H), 7.19–7.10 (m, 2 H), 6.87 (dd, J = 17.6, 10.9 Hz, 1 H),
5.84 (dd, J = 17.6, 0.9 Hz, 1 H), 5.30 (dd, J = 10.9, 0.9 Hz, 1 H),
3.93 (s, 3 H).
Chin.
J.
Org.
Chem.
2021,
41,
in
press,
DOI:
10.6023/cjoc202101019.
(24) For a similar Pd-catalyzed C–O bond-forming reaction using
vinyltrimethoxysilane and electron-deficient aryl halides, see:
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7, 2645.
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(27) General Procedure 1
General Procedure 2
In a nitrogen-filled glove box, aromatic halide (0.2 mmol, 1.0
equiv), TBAT (270 mg, 0.5 mmol, 2.5 equiv), NiCl2(glyme) (4.4
mg, 0.02 mmol, 10 mol%), and DMA (1.0 mL) were charged to an
8 mL vial equipped with a magnetic stirrer bar. The vinyltrime-
thoxysilane (59.1 mg, 0.4 mmol, 2.0 equiv) was added. The vial
was removed from the glove box, and the reaction mixture was
stirred at rt (35 °C) for 12 h. The reaction mixture was then
diluted with EtOAc and washed with water. The organic phase
was dried over Na2SO4, filtered, and concentrated, and the
residue was purified by column chromatography on silica gel to
give the product.
In a nitrogen-filled glove box, aromatic halide (0.2 mmol, 1.0
equiv), 18-crown-6 (121.0 mg, 0.46 mmol, 2.3 equiv), KOMe
(32.2 mg, 0.46 mmol, 2.3 equiv), NiCl2(glyme) (4.4 mg, 0.02
mmol, 10 mol%), and DMF (1.0 mL) were charged to an 8 mL vial
equipped with a magnetic stirrer bar. The vinyltrimethoxysi-
lane (68.0 mg, 0.46 mmol, 2.3 equiv) was added. The vial was
removed from the glove box, and the reaction mixture was
stirred at rt (35 °C) for 12 h. The reaction mixture was then
2-Vinylnaphthalene (3b)
Using general procedure 2: white solid, 25.5 mg, yield: 83%. 1H
NMR (400 MHz, CDCl3):  = 7.85–7.79 (m, 3 H), 7.76 (s, 1 H),
7.65 (dd, J = 8.6, 1.7 Hz, 1 H), 7.50–7.42 (m, 2 H), 6.90 (dd, J =
17.6, 10.9 Hz, 1 H), 5.89 (dd, J = 17.6, 0.8 Hz, 1 H), 5.35 (dd, J =
10.9, 0.8 Hz, 1 H).
© 2021. Thieme. All rights reserved. Synlett 2021, 32, A–E