Nickel(II)/N-Heterocyclic Carbene Catalyzed Desulfinylative Arylation by C?S Cleavage of Aryl Sulfoxides with Phenylboronic Acids

Article abstract of DOI:10.1002/adsc.202000531

Suzuki-Miyaura coupling of haloarenes is the most widely used protocol for the synthesis of biphenyls. Organosulfur compounds are promising electrophiles since they are abundant in nature and versatile in organic synthesis. We report here the desulfinylative Suzuki-Miyaura coupling of aryl sulfoxides with phenylboronic acids using bench-stable nickel/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily prepared from common commercial chemicals. The method is applicable to both symmetric and unsymmetric aryl sulfoxides, and a range of biphenyls bearing various functional groups were obtained in up to 94% yield. (Figure presented.).

Full text of DOI:10.1002/adsc.202000531

Title: Nickel(II)/N-Heterocyclic Carbene Catalyzed Desulfinylative
Arylation by C-S Cleavage of Aryl Sulfoxides with Phenylboronic
Acids
Authors: Xiaowen Yi, Kai Chen, Junjun Guo, Wei Chen, and Wanzhi
Chen
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10.1002/adsc.202000531
Advanced Synthesis & Catalysis
Very Important Publication
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Nickel(II)/N-Heterocyclic Carbene Catalyzed Desulfinylative
Arylation by C-S Cleavage of Aryl Sulfoxides with
Phenylboronic Acids
Xiaowen Yi,a Kai Chen, Junjun Guo, Wei Chen, and Wanzhi Chen*
Department of Chemistry, Zhejiang University, 38 Zheda Road, Hangzhou, 310027, China
Email: chenwzz@zju.deu.cn
Note: aPresent address: School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
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))
Abstract. Suzuki-Miyaura coupling of haloarenes is the
most widely used protocol for the synthesis of biphenyls.
Organosulfur compounds are promising electrophiles
since they are abundant in nature and versatile in organic
synthesis. We report here the desulfinylative Suzuki-
Miyaura coupling of aryl sulfoxides with phenylboronic
acids
using
bench-stable
nickel/5-(2,4,6-
triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the
catalyst. The ligands are readily prepared from common
commercial chemicals. The method is applicable to both
symmetric and unsymmetric aryl sulfoxides, and a range
of biphenyls bearing various functional groups were
obtained in up to 94% yield.
Keywords: N-heterocyclic carbene; nickel; Suzuki-
Miyaura coupling; phenylboronic acids; sulfoxide
Biphenyls are a quite privileged structural scaffold.
Biphenyl units have been found to exist in many
important pharmaceuticals, agrochemicals, and
materials.[1] One of the most practical and efficient
approaches to construct biphenyls is Suzuki-Miyaura
cross-coupling, which frequently uses organic halides
as the electrophilic component. However, due to the
undesirable halogen-based contamination and
relatively high cost,[2] significant efforts have been
devoted to developing alternatives to organic halides,
such as aryl ethers,[3] aryl esters,[4] aryl amides,[5]
nitroarenes,[6] dimethyl aryl amines,[7] aryl nitriles,[8]
and simple ketones.[9]
Organosulfur
compounds
are
promising
electrophiles in cross-coupling reactions due to their
abundance in nature and versatility in organic
synthesis.[10] The employment of organosulfur
compounds including even unactivated aryl sulfides
to construct C-C bonds has attracted attention in the
recent decade.[11]
Scheme 1. Formation of C-C bonds via C-S Bonds
Cleavage.
1
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10.1002/adsc.202000531
Advanced Synthesis & Catalysis
In this context, palladium catalyzed Suzuki-coupling efficiencies in the activation and functionalization of
of arylsulfonium salts containing activated C-S bond inert C-O, C-N, and C-Cl bonds.[4,7,16] We have
were firstly reported by Liebeskind and co-workers recently shown that the NHC ligands having a
(Scheme 1a).[11a] Later, palladium catalyzed arylation imidazolylidene[1,5-a]pyridine skeleton promote
of activated heteroaromatic thioethers was described palladium-catalyzed
denitrative
coupling
of
by the same group (Scheme 1b).[11b] Although the nitroarenes.[6b-c,17] We envisioned that the well-
protocol is highly effective, the scope of thioethers designed N-heterocyclic carbenes which show strong
was restricted to electron-deficient heteroaromatic σ-donating ability and suitable steric hindrance could
thioethers. Thioesters, thioalkynes, and sulfonyl also promote the desulfinylative coupling of C-S bond
chlorides were also applied to react with boronic acids of aryl sulfoxides. Herein, we disclose the NHC/Ni
to construct C-C bonds.[11c-f] The earlier progress in catalyzed Suzuki-Miyaura coupling of aryl sulfoxides
the metal-catalyzed C-S activation and application of leading to a number of biphenyls in moderate to
organosulfur compounds as electrophilic reagents in excellent yields.
C-C formation reactions were summarized.[11g-k] In
We have shown that NHCs with
a
2013, Willis and Shi et al. independently reported a imidazolylidene[1,5-a]pyridine skeleton are efficient
rhodium-catalyzed Suzuki-Miyaura coupling of aryl for palladium-catalyzed C-N activation of nitroarenes
sulfides (Scheme 1c).[12] The C-S bond cleavage was and successive coupling.[6b-c,17] A series of NHC
achieved via an acetyl group as a directing group. ligand precursors listed in Scheme
2
were
Several challenges are associated with this prepared,[6b] and their performance for nickel-
transformation such as the inertness of C-S bond of catalyzed arylation of aryl sulfoxides were tested.
aryl sulfides toward oxidative addition and the ease of Initially, to screen the reaction conditions, the
thiolate poisoning of transition metal catalyst. Aryl reaction
of
diphenyl
sulfoxide
and
4-
sulfoxides and sulfones as alternatives are more methoxyphenylboronic acid was chosen as the model
electron-deficient and thus more reactive.[13] Recently, reaction using Ni(acac)2/HL1.Cl as the catalyst in 1,4-
Yorimitsu et al. reported a nickel-catalyzed Negishi dioxane at 130 C. To our delight, HL1.Cl bearing a
o
cross-coupling of aryl sulfoxides with arylzinc halides N-2,6-dimethylphenyl substituent (R1 = R2 = Me) was
giving biphenyls in good yields (Scheme 1d).[14] More a suitable ligand and the desulfinylative Suzuki-
recently, several groups described the Suzuki- Miyaura
coupling
successfully
gave
4-
Miyaura coupling of sulfones via C-SO2 bond methoxybiphenyl 3aa in 49% yield (Table 1, entry 1).
cleavage of aryl and alkenyl sulfones using Inspired by this result, we next examined other NHC
nickel,[15a,b]
palladium[15c]
or
bimetallic ligands. When the two ortho methyl were replaced by
palladium/rhodium catalysts[15d] (Scheme 1e).
two bulkier ethyl groups or isopropyl groups (R1 = R2
i
= Et, Pr), the yields were sharply decreased to below
20% (Table 1, entries 2-4). The use of less sterically
hindered ligand, HL6.Cl, also gave low yield of 3aa
(Table 1, entry 6). We speculate that the bulkiness of
HL1.Cl just meets the requirement of C-S oxidative
addition and C-C reductive elimination. HL5.Cl
bearing fluoro substituents at two ortho positions (R1
= R2 = F) also resulted in low conversion (Table 1,
entry 5). These results illustrate that two ortho methyl
groups are needed to reach satisfactory yield, and the
para-methyl plays a negative role (Table 1, entry 2 vs
entry 4). HL7.Cl containing a less bulky 2,6-
dimethylphenyl group at 5-position showed lower
activity, and the desired compound was obtained in
diminished yield (Table 1, entry 7). Obviously, the 5-
(2,4,6-triisopropylphenyl) moiety plays an important
role on the stabilization of active nickel species, and
promotes the reductive elimination process. For
comparison, the commonly used bulky NHC ligands
such as SIPr, IPr, IMes, and IPr* were explored,
and they were found to be less efficient (Table 1,
entries 8-11). The influences of bases were tested. In
the presence of K3PO4 and CsF, no desired product
was observed. The arylation proceeded in 28% yield
when KOH was used (Table 1, entries 12-14).
Screening of solvents illustrated that the etheric
solvents are more appropriate for the reaction (Table
Scheme 2. NHC Ligand Precursors.
To the best of our knowledge, there are no reports
on desulfinylative coupling of aryl sulfoxides with
phenylboronic acids thus far. Sterically hindered N-
heterocyclic carbenes (NHCs) have shown their
1, entries 15-17). Ni(OAc)2 and NiBr2 were also
applied to the coupling, but both of them were almost
inactive (Table 1, entries 18-19). We found that
2
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10.1002/adsc.202000531
Advanced Synthesis & Catalysis
increasing the loading of Ni(acac)2 to 7.5 mol% from substituents such as alkyl, alkoxy, thioether,
5.0 mol% can further improve the reaction yield to trimethylsilyl, and phenyl groups were successfully
89% (Table 1, entry 20). The Ni(acac)2/HL1.Cl coupled affording the corresponding biphenyl
catalyst was not much sensitive to air. When the derivatives 3aa-3ai in 35-94% yields. Notably,
reaction was performed in air, the desired product 3aa reactive functional groups such as thioether and
could also be obtained in 45% yield. Finally, when trimethylsilyl substituents are compatible, giving 3ag
the reaction time was extended to 36 hours, the yield and 3ah in comparable yields. However, the sterically
could be further increased to 94% with a trace amount hindered
2,2'-sulfinylbis(1,3,5-trimethylbenzene)
of diphenyl sulfide detected. The detailed failed to react, and only trace amount of coupling
optimizations were listed in Tables S1-S5 (supporting product 3ae was observed. The result indicates that
information). In these reactions, a small amount of the desulfinylative coupling is sensitive to steric
homocoupling product of arylboronic acids in less hindrance of aryl sulfoxides. The reactivities of halo-
than 10% yield was often observed.
containing aryl sulfoxides were tested. Ar-F bond
maintains in product 3aj, while Ar-Cl bond was not
very compatible due to its competitive reactivity. In
the case of 4,4'-sulfinylbis(chlorobenzene), the
reaction gave a complicated mixture. 3ak was
afforded in only 10% yield as detected by GC
analysis, and about 26% hydrodechlorinated product
1-chloro-4-(phenylsulfinyl)benzene together with
Table 1. Optimization of Reaction Conditionsa
15%
4',4'''-sulfinylbis(4-methoxy-1,1'-biphenyl)
NHC
ligand
Entry
Base
Solvent Yieldb %
which was resulting from the coupling of C-Cl bond
were observed. Aryl sulfoxides bearing an electron-
withdrawing group such as trifluoromethyl were
successfully transformed to 3al and 3am in 77% and
85% yields, respectively. These transformations are
very important since CF3 often exists in many
pharmaceutically structures. However, the cyano-
containing aryl sulfoxide showed low yield possibly
because of the high sensitivity of the cyano group
toward strong bases. Under the standard conditions,
the unsymmetric aryl sulfoxide was applied to the
desulfinylative coupling. Unsymmetric 4-methyl-4'-
(trifluoromethyl)-1,1'-biphenyl 1q, was successfully
transformed to 3al and 3ab in 77% and 12% yields,
respectively, which showed that the C-S bond at the
electron-deficient side is weaker and its
desulfinylative coupling is preferred.
1
2
3
4
5
6
7
8
KOtBu dioxane 49
KOtBu dioxane 19
KOtBu dioxane 11
HL1.Cl
HL2.Cl
HL3.Cl
HL4.Cl
HL5.Cl
HL6.Cl
HL7.Cl
SIPr.Cl
IMes.Cl
IPr*.Cl
IPr.Cl
KOtBu dioxane
7
KOtBu dioxane 13
KOtBu dioxane 10
KOtBu dioxane 32
KOtBu dioxane
6
9
KOtBu dioxane 12
KOtBu dioxane <5
KOtBu dioxane 16
10
11
12
13
14
15
16
17
18
19
20
HL1.Cl
HL1.Cl
HL1.Cl
HL1.Cl
HL1.Cl
HL1.Cl
IPr.Cl
K3PO4
CsF
dioxane
dioxane
0
0
KOH
dioxane 28
KOtBu toluene
KOtBu THF
5
35
KOtBu tBuOH <5
KOtBu dioxane <5c
KOtBu dioxane <5d
KOtBu dioxane 89e 45f
KOtBu dioxane 94g
Table 2. Scope of Aryl Sulfoxidesa
IPr.Cl
HL1.Cl
HL1.Cl
21
a
1a (0.3 mmol, 1.0 equiv), 2a (1.5 equiv), Ni(acac)2 (5
mol%), KOtBu (3.0 equiv), NHC ligand (10 mol%),
dioxane (1.5 mL), N2, 24 h. Determined by H NMR
analysis using 1,3,5-trimethoxybenzene as an internal
standard. c Ni(OAc)2 instead of Ni(acac)2. d NiBr2 instead of
b
1
e
Ni(acac)2. Ni(acac)2 (7.5 mol%), NHC ligand (15 mol%),
f
24 h. Ni(acac)2 (7.5 mol%), NHC ligand (15 mol%), 24 h,
in air. g Ni(acac)2 (7.5 mol%), NHC ligand (15 mol%), 36 h,
isolated yield.
After optimization studies, we set out to explore the
substrate scope of the arylation reaction. At first,
various symmetric aryl sulfoxides were investigated,
and the scope of aryl sulfoxides is presented in Table
2. Under the optimized conditions, a variety of
substituted symmetric aryl sulfoxides were
transformed to biphenyl derivatives 3aa-3ap in up to
94% yield. Aryl sulfoxides bearing electron-donating
3
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10.1002/adsc.202000531
Advanced Synthesis & Catalysis
a
1 (0.3 mmol, 1.0 equiv), 2 (1.5 equiv), Ni(acac)2 (7.5
a
mol%), KOtBu (3.0 equiv), HL1.Cl (15 mol%), dioxane
(1.5 mL), N2, 36 h, isolated yields. Toluene instead of
1 (0.3 mmol, 1.0 equiv), 2 (1.5 equiv), Ni(acac)2 (7.5
mol%), KOtBu (3.0 equiv), HL1.Cl (15 mol%), dioxane
(1.5 mL), N2, 36 h, isolated yields. A gram-scale reaction
b
b
dioxane was used as the solvent.
using 1.01 g of diphenyl sulfoxide, and 1.14 g of 4-
methoxyphenylboronic acid under the optimized
conditions, isolated yield. c Determined by GC analysis.
We next explored the scope of the desulfinylative
Suzuki-Miyaura coupling with respect to arylboronic
acids. The results for phenyl sulfoxide and 4,4'-
dimethoxy diphenylsulfoxide were summarized in
Table 3. Arylboronic acids containing different
functional groups at o-, m-, and p-positions could
undergo the reaction giving the corresponding
products in 29-84% yields. Generally, electron-rich
arylboronic acids containing alkyl, alkoxyl, amino,
and phenyl substituents are favorable to the arylation.
The fluoro and amino groups were not affected, and
the corresponding products 3aj and 3bd were
obtained in 84% and 78% yields, respectively.
However, electron-deficient arylboronic acid showed
diminished yield giving 3al in 29% yield. As for
polycyclic arylboronic acids, biaryl derivatives 3ao,
3ap, 3bg, and 3bh were produced in moderate yields.
The
reaction
of
unsymmetric
4-
(methylsulfinyl)benzene
with
methoxyphenylboronic acid was also tested under the
same conditions. The desired product 4-
methoxybiphenyl was obtained in 14% yield based on
1H NMR analysis. Most (methylsulfinyl)benzene
remained unreacted. It was believed that the C(sp2)-
(S=O) bonds of alkyl aryl sulfoxides would be more
electron-rich and less reactive toward oxidative
addition to electron-rich Ni(0) species.[18] Finally, we
examined the possibility of heteroaryl sulfoxides.
Unfortunately,
the
coupling
of
and
3-((2,6-
2,2'-
dimethylphenyl)sulfinyl)pyridine
sulfinyldithiophene failed.
Based on the previous literature reports,[13-14,19]
a
plausible catalytic cycle in Scheme 3 was proposed.
The reaction of Ni(acac)2 and HL1.Cl would in situ
generate a highly electron-rich NHC-Ni(0) species
under basic conditions. Oxidative addition of Ar2SO
toward (NHC)Ni(0) would form intermediate I.
Subsequent transmetalating between the resulting
intermediate I and arylboronic acid would give II.
Finally, the target product would be generated
through reductive elimination of II.
Table 3. Scope of Arylboronic Acidsa
4
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10.1002/adsc.202000531
Advanced Synthesis & Catalysis
[1] a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-
2483; b) D. G. Brown, J. Bostrom, J. Med. Chem. 2015,
59, 4443-4458; c) A. Biffis, P. Centomo, A. Del Zotto,
M. Zecca, Chem. Rev. 2018, 118, 2249-2295.
[2] A. M. Norberg, L. Sanchez, J. R. Maleczka, Curr. Opin.
Drug Discovery Dev. 2008, 11, 853-869.
[3] D. Yu, B. Li, Z. Shi, Acc. Chem. Res. 2010, 43, 1486-
1495.
[4] T. Ben Halima, W. Zhang, I. Yalaoui, X. Hong, Y.
Yang, K. N. Houk, S. G. Newman, J. Am. Chem. Soc.
2017, 139, 1311-1318.
[5] G. Meng, M. Szostak, Org. Lett. 2018, 20, 6789-6793.
[6] a) M. R. Yadav, M. Nagaoka, M. Kashihara, R.-L.
Zhong, T. Miyazaki, S. Sakaki, Y. Nakao, J. Am. Chem.
Soc. 2017, 139, 9423-9426; b) K. Chen, W. Chen, X.
Yi, W. Chen, M. Liu, H. Wu, Chem. Commun. 2019,
55, 9287-9290; c) M. Kashihara, R.-L. Zhong, K.
Semba, S. Sakaki, Y. Nakao, Chem. Commun. 2019, 55,
9291-9294.
Scheme 3. Plausible catalytic cycle.
In summary, we have developed an efficient
nickel/NHC-catalyzed Suzuki-Miyaura coupling of
aryl sulfoxides. The key to success is the rational
design of NHC ligands which show strong donating
ability and suitable steric hindrance. The NHC ligands
[7] Z. Cao, S. Xie, H. Fang, Z. Shi, J. Am. Chem. Soc.
2018, 140, 13575-13579.
are
generated
in
situ
from
5-(2,4,6-
[8] D. Yu, M. Yu, B. Guan, B. Li, Y. Zheng, Z. Wu, Z. Shi,
triisopropylphenyl)imidazoylidene[1,5-a]pyridine and
their precursors are readily prepared from inexpensive
and common commercial reagents. A number of
biphenyls were obtained in moderate to excellent
yields. However, heterocyclic coupling partners are
still limited. Further improvement of the NHC ligands
is needed to expand the scope of heteroaryl sulfoxides
as well as heteroarylboronic acids.
Org. Lett. 2009, 11, 3374-3377.
[9] Y. Xia, J. Wang, G. Dong, J. Am. Chem. Soc. 2018,
140, 5347-5351.
[10] a) R. J. Cremlyn, An introduction to organosulfur
chemistry, Vol. 8, Wiley New York, 1996; b) Q. A.
Acton, Sulfur compounds: advances in research and
application, Ed.; Scholarly Eds., Atlanta, GA, 2012.
[11] a) J. Srogl, G. D. Allred, L. S. Liebeskind, J. Am.
Chem. Soc. 1997, 119, 12376-12377; b) L. S.
Liebeskind, J. Srogl, Org. Lett. 2002, 4, 979-981; c) L.
S. Liebeskind, J. Srogl, J. Am. Chem. Soc. 2000, 122,
11260-11261; d) C. Savarin, J. Srogl, L. S. Liebeskind,
Org. Lett. 2001, 3, 91-93; e) Y. Yu, L. S. Liebeskind, J.
Org. Chem. 2004, 69, 3554-3557; f) H. Prokopcova, C.
O. Kappe, Angew. Chem. 2008, 120, 3732-3734;
Angew. Chem. Int. Ed. 2008, 47, 3674-3676; g) S. R.
Dubbaka, P. Vogel, Angew. Chem. 2005, 117, 7848-
7859; Angew. Chem. Int. Ed. 2005, 44, 7674-7684; h)
T.-Y. Luh, Z.-J. Ni, Synthesis 1990, 1990, 89-103; i) S.
G. Modha, V. P. Mehta, E. V. Van der Eycken, Chem.
Soc. Rev. 2013, 42, 5042-5055; j) K. Gao, S. Otsuka, A.
Baralle, K. Nogi, H. Yorimitsu, A. Osuka, J. Synth.
Org. Chem., Jpn. 2016, 74, 1119-1127; k) S. Otsuka, K.
Nogi, H. Yorimitsu, Top. Curr. Chem. 2018, 376, 13.
Experimental Section
General Procedure for the Suzuki-Miyaura
Coupling of Aryl Sulfoxides
To an oven-dried tube equipped with a magnetic
stirring bar were added sequentially diaryl sulfoxide 1
(0.3 mmol), boronic acid 2 (0.45 mmol), Ni(acac)2
(5.8 mg, 0.0225 mmol), HL1·Cl (20.7 mg, 0.045
mmol), KOtBu (101 mg, 0.9 mmol), and dioxane (1.5
mL) under N2 atmosphere. The reaction mixture was
stirred at room temperature for 30 minutes, and then
o
heated by a mantle (IKA RCT B S025) at 130 C for
36 hours. The reaction mixture was cooled to room
temperature, and then it was passed through a short
pad of celite with CH2Cl2. The solution was
concentrated in vacuo. The residue was purified by
silica gel column chromatography to give the
coupling product 3.
[12] a) J. F. Hooper, R. D. Young, I. Pernik, A. S. Weller,
M. C. Willis, Chem. Sci. 2013, 4, 1568-1572; b) F. Pan,
H. Wang, P.-X. Shen, J. Zhao, Z.-J. Shi, Chem. Sci.
2013, 4, 1573-1577.
Acknowledgements
[13] Y. Yoshida, S. Otsuka, K. Nogi, H. Yorimitsu, Org.
Lett. 2018, 20, 1134-1137.
We thank the National Natural Science Foundation (NSF) of
China (21572203) for financial support.
[14] K. Yamamoto, S. Otsuka, K. Nogi, H. Yorimitsu,
ACS Catal. 2017, 7, 7623-7628.
References
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000531
Advanced Synthesis & Catalysis
[15] a) Z. T. Ariki, Y. Maekawa, M. Nambo, C. M.
Crudden, J. Am. Chem. Soc. 2018, 140, 78-81; b) L.
Gong, H.-B. Sun, L.-F. Deng, X. Zhang, J. Liu, S.
Yang, D. Niu, J. Am. Chem. Soc. 2019, 141, 7680-
7686; c) J. Moran, C. Rowley, A. Sau, P. Chatelain,
Angew. Chem. 2005, 131, 15101-15105; Angew. Chem.
Int. Ed. 2019, 58, 14959-14963; d) J. Fukuda, K. Nogi,
H. Yorimitsu, Org. Lett. 2019, 21, 8987-8991.
[16] a) P. Lei, G. Meng, S. Shi, Y. Ling, J. An, R. Szostak,
M. Szostak, Chem. Sci. 2017, 8, 6525-6530; b) S. Shi,
P. Lei, M. Szostak, Organometallics 2017, 36, 3784-
3789; c) P. Lei, G. Meng, M. Szostak, ACS Catal. 2017,
7, 1960-1965; d) G. Altenhoff, R. Goddard, C. W.
Lehmann, F. Glorius, J. Am. Chem. Soc. 2004, 126,
15195-15201; e) M. G. Organ, S. Calimsiz, M. Sayah,
K. H. Hoi, A. J. Lough, Angew. Chem. 2009, 121,
2419-2423; Angew. Chem. Int. Ed. 2009, 48, 2383-
2387; f) S. Meiries, A. Chartoire, A. M. Slawin, S. P.
Nolan, Organometallics 2012, 31, 3402-3409.
[17] W. Chen, K. Chen, W. Chen, M. Liu, H. Wu, ACS
Catal. 2019, 9, 8110-8115.
[18] Y. Yoshida, K. Nogi, H. Yorimitsu, Synlett 2017, 28,
2561-2564.
[19] F. Takahashi, K. Nogi, H. Yorimitsu, Org. Lett. 2018,
20, 6601-6605.
6
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Advanced Synthesis & Catalysis
COMMUNICATION
Nickel(II)/N-Heterocyclic Carbene Catalyzed
Desulfinylative Arylation by C-S Cleavage of Aryl
Sulfoxides with Phenylboronic Acids
Adv. Synth. Catal. Year, Volume, Page – Page
Xiaowen Yi, Kai Chen, Junjun Guo, Wei Chen,
Wanzhi Chen*
7
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