Decarbonylative thioetherification by nickel catalysis using air- and moisture-stable nickel precatalysts

Article abstract of DOI:10.1039/c8cc00271a

A general, highly selective method for decarbonylative thioetherification of aryl thioesters by C-S cleavage is reported. These reactions are promoted by a commercially-available, user-friendly, inexpensive, air- and moisture-stable nickel precatalyst. The process occurs with broad functional group tolerance, including free anilines, cyanides, ketones, halides and aryl esters, to efficiently generate thioethers using ubiquitous carboxylic acids as ultimate cross-coupling precursors (cf. conventional aryl halides or pseudohalides). Selectivity studies and site-selective orthogonal cross-coupling/thioetherification are described. This thioester activation/coupling has been highlighted in the expedient synthesis of biorelevant drug analogue. In light of the synthetic utility of thioethers and Ni(ii) precatalysts, we anticipate that this user-friendly method will be of broad interest.

Full text of DOI:10.1039/c8cc00271a

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: C. Liu and M.
Szostak, Chem. Commun., 2018, DOI: 10.1039/C8CC00271A.
This is an Accepted Manuscript, which has been through the
Volume 52 Number
1 4 January 2016 Pages 1–216
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Accepted Manuscripts are published online shortly after
Chemical Communications
www.rsc.org/chemcomm
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
=
3
rsc.li/chemcomm

Please do not adjust margins
ChemComm
Page 1 of 4
View Article Online
DOI: 10.1039/C8CC00271A
Chemical Communications
COMMUNICATION
Decarbonylative Thioetherification by Nickel Catalysis using Air-
and Moisture-Stable Nickel Precatalysts
Chengwei Liua and Michal Szostaka,*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
general, highly selective method for decarbonylative Yorimitsu and co-workers have shown that Pd-NHC systems
thioetherification of aryl thioesters by C–S cleavage is reported. catalyze the coupling of aromatic thioethers with N- and C-
These reactions are promoted by a commercially-available, user- nucleophiles.9 In another important development, Niwa,
friendly, inexpensive, air- and moisture-stable nickel precatalyst. Hosoya and co-workers established the feasibility of Rh-
The process occurs with broad functional group tolerance, catalyzed decarbonylative borylation of thioesters.10 The
including free anilines, cyanides, ketones, halides and aryl esters, recent surge of efforts to capture sulfur intermediates in
to efficiently generate thioethers using ubiquitous carboxylic acids metal-free pathways11 engenders the appeal of assembling
as ultimate cross-coupling precursors (cf. conventional aryl halides thioethers from carboxylic acid-based substrates using robust,
or pseudohalides). Selectivity studies and site-selective orthogonal operationally-simple protocols that could be widely adapted in
cross-coupling/thioetherification are described. This thioester various areas of chemical science.
activation/coupling has been highlighted in the expedient
In the past decade, there has been an increasing interest in
synthesis of biorelevant drug analogues. In light of the synthetic nickel catalysis due to more facile oxidative addition,
utility of thioethers and Ni(II) precatalysts, we anticipate that this abundance and economic advantages compared with Pd
user-friendly method will be of broad interest.
catalysis.12 Generally speaking, the use of air- and moisture-
stable precatalysts is strongly preferred in modern cross-
coupling applications.13 In this context, the groups of
Monteiro,14 Percec,15 Buchwald,16 Jamison,17 Doyle,18
Monfette19 and others15–19 have reported well-defined Ni(II)
The thioether functional group represents one of the
privileged structural motifs in the synthesis of pharmaceuticals
(Fig. 1A).1,2 Most synthetic disconnections for the synthesis of
aryl thioethers capitalize on transition-metal-catalyzed cross-
coupling of aryl halides or pseudohalides with thiols (Fig. 1B).3,4
Recently, significant progress has been made in the
development of transition-metal-catalyzed decarbonylative
processes that utilize ubiquitous carboxylic acids as ultimate
cross-coupling precursors in the oxidant free, redox-neutral
decarbonylative pathway.5 Carboxylic acids are among the
most appealing chemical building blocks in organic synthesis.5b
Of note, carboxylic acids are (1) cheaper and there are more
carboxylic acids commercially available than aryl halides; (2)
derived from a different pool of precursors than aryl halides
and pseudohalides; (3) inert to a variety of reaction conditions
allowing for ring prefunctionalization.6 Likewise, significant
effort has been devoted to the cross-coupling of inert C–S
bonds.7 Notably, Morandi and co-workers have developed a
versatile method for carbon-sulfur bond metathesis,8 while
precatalysts, which enable
a variety of cross-coupling
transformations. The fact that the use of robust, bench-stable
Ni(II) precatalysts enables broad applications of metal catalysis
in industrial research13 in lieu of the limited options available
with air-sensitive and capricious Ni(0)-complexes.
Inspired by our recent studies in decarbonylative
olefination,20 arylation,21 cyanation22 and phosphorylation23 of
amides,24 in this report we communicate our findings on
decarbonylative thioetherification of aryl thioesters by
selective C–S cleavage enabled by user-friendly, air- and
moisture-stable nickel precatalysts (Fig. 1C). While this work
was in progress, a Ni(0)-catalyzed decarbonylative thioether
synthesis by C–S cleavage using a combination of air-sensitive
Ni(cod)2 (10 mol%) and PCy3 (20 mol%) was reported.25 Since
our method (1) utilizes Ni(II) precatalysts that are air-stable,
easy to handle and manipulate, (2) is significantly broader in
scope, and (3) enables the use of operationally-simple and
robust decarbonylative thioetherification for wide applications
within both industry and academia, we anticipate that the
protocol will be of general interest to the broad synthetic
community.1–4,13
aDepartment of Chemistry,Rutgers University, 73 Warren Street, Newark, NJ 07102,
United
States. Fax:
(+1)-973-353-1264;
Tel:(+1)-973-353-532. E-mail:
michal.szostak@rutgers.edu. Homepage: http://chemistry.rutgers.edu/szostak/
†Electronic Supplementary Informaꢀon (ESI) available: Experimental details and
characterization data. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 2018
Chem. Commun., 2018, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 4
View Article Online
DOI: 10.1039/C8CC00271A
COMMUNICATION
Chemical Communications
A. Examples of pharmaceutically-relevant aryl thioethers
Table
1 Reaction Optimization: Ni-Catalyzed Decarbonylative
Thioetherificationa
O
NHMe
N
O
N
H
S
S
N
O
HO
N
Me
N
HN
H2N
N
S
Axitinib
VEGF inhibitor
Thymitaq
anticancer
NMe2
Quetiapine
atypical antipsychotic
Yield
(%)b
>95
>95
<2
N
Entry
Catalyst
Base
T (°C)
S
S
1
2
3
4
5
Ni(dppp)Cl2
Ni(PCy3)2Cl2
Ni(dppp)Cl2
Ni(PCy3)2Cl2
-
Na2CO3
Na2CO3
-
160
160
160
160
160
140
140
140
140
140
140
140
140
140
140
140
140
140
160
120
O
Cl
N
OH
O
N
Me
S
-
<2
<2
Chloropromazine
dopamine antagonist
AZD4407
Me
lipogenase inhibitor
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
K2CO3
6
7
8
9
Ni(dppp)Cl2
Ni(PCy3)2Cl2
Ni(PPh3)2Cl2
Ni(dppe)Cl2
Ni(dppf)Cl2
Ni(OAc)2
>95
>95
43
>95
18
B. Traditional metal-catalyzed synthesis of aryl thioethers
cat. [Pd], [Ni], [Cu], RSH
X
S
R
Ar
Ar
-X
10
11
12
13
14
15c
16d
17e
18f
19f
20
X = I, Br, Cl, OR', N2+, B, Si
<5
C. Decarbonylative thioetherification by Ni catalysis: this study
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
Ni(PCy3)2Cl2
27
<5
15
87
>95
>95
27
>95
52
O
Cs2CO3
K3PO4
[Ni], -CO
S
R
R
S
Ar
Ar
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
O
thioesters
oxidative
Aryl thioethers
reductive
Ar
OH
carboxylic acid
precursors
addition
elimination
[Ni]
R
O
[Ni]
decarbonylation
R
S
Ar
S
Ar
-CO
aConditions: thioester (1.0 equiv), catalyst (10 mol%), base (1.5
selective C S cleavage modular, air-stable Ni precatalyst
carboxylic acid precursors broad tolerance high generality
equiv), 1,4-dioxane (0.20 M), T, 15 h. GC/1H NMR yields. toluene.
b
c
dCH3CN. eDMF. fcatalyst (5 mol%). See ESI for details.
Decarbonylative Coupling via Selective C S Cleavage
Fig. 1 (a) Examples of pharmaceutically important aryl thioethers.
(b) Conventional synthesis. (c) Decarbonylative thioetherification
using air- and moisture-stable Ni precatalysts (this study).
The reaction exhibits broad substrate scope (Scheme 1).
Electron-rich (2b-c) and electron-deficient (2d) substrates
performed well in this protocol. Notable examples include
The reaction was optimized using S-phenyl benzothioate as
halides
(2e-f) and electrophilic functional groups (2g-i),
a
model substrate. Key optimization experiments are
summarized in Table 1. Using our optimized conditions,
Ni(dppp)Cl2, (10 mol%), Na2CO3 (1.5 equiv), dioxane, 160 C, S-
providing handles for further functionalization. Ortho-
substitution was well-tolerated under these conditions (2j-k).
Furthermore, this protocol could be extended to polyaromatic
°
phenyl benzothioate undergoes selective C–S insertion/CO
extrusion in excellent yield (entry 1). Under these conditions,
Ni(PCy3)2Cl2 is also a highly effective catalyst (entry 2). As
expected, no reaction is observed in the absence of base
(entries 3-4) or nickel precatalyst (entry 5). Examination of
various reaction parameters revealed a significant dependence
on the Ni(II) complex used (entries 6-10), with Ni(dppp)Cl2,
Ni(dppe)Cl2, and Ni(PCy3)2Cl2 showing similar performance. As
expected, no reaction was observed in the absence of
phosphine ligand (entry 11). An extensive screen of bases
revealed that the best results were obtained with Na2CO3
(entries 12-14). Dioxane was identified as the optimal solvent
(entries 15-17). We were pleased to find that decreasing the
nickel loading to 5 mol% delivered the product under the
optimized conditions (entries 18-19). Low conversions were
observed in the presence of oxygen (not shown). Finally, we
(
2l), heterocyclic (2m-n) and vinyl substrates (2o), providing
the desired products in good to excellent yields. Finally, the
scope of the thiol component was briefly examined (Table 2). A
selection of electron-rich (entry 2), electron-deficient (entry 3),
halide-containing (entry 4) and sterically-hindered (entry 5)
substrates were converted into the desired thioethers in high
yields. Important from a practical point of view, all of these
reactions were conveniently set-up on a bench-top, which
provides
a
very attractive feature of this protocol.13–19
Furthermore, the scope supersedes the Ni(cod)2 system25 in
that cyanides, ketones, halides, unprotected anlines (vide
infra) and aryl esters (vide infra) are readily tolerated.
Preliminary studies demonstrate that cross-coupling of an
aryl-alkyl thioester is also feasible (Scheme 2), providing
another advantage of this user-friendly method. Note that
alkyl thioesters are not tolerated using air-sensitive Ni(cod)2.25
Studies to expand the scope of aryl–alkyl coupling to chiral
thioesters are ongoing and will be reported in due course.
To investigate the potential utility of this cross-coupling
method, we tested this protocol in the rapid derivatization of
note that substantial conversion was observed as 120 °C,
consistent with facile decarbonylation by this catalytic system
(entry 20).
2 | Chem. Commun., 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 2018
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 3 of 4
View Article Online
DOI: 10.1039/C8CC00271A
Chemical Communications
COMMUNICATION
flufenamic acid, a selective COX-2 inhibitor (Scheme 3).26 As
shown, the reaction proceeded uneventfully, delivering the
desired thioether product in high overall yield.10
aConditions: thioester (1.0 equiv), Ni(dppp)Cl2 (10 mol%), Na2CO3 (1.5 equiv),
dioxane (0.20 M), 160 °C, 15 h. bIsolated yields. See ESI for details.
Scheme 2 Ni-Catalyzed Decarbonylative Thioetherification of
S-Alkyl Benzothioate
Scheme 1 Substrate Scope: Ni-Catalyzed Decarbonylative
Thioetherificationa,b
Scheme 3 Expedient Synthesis of Flufenamic Acid Thioether
Scheme 4 Selective Decarbonylative Thioetherification
aConditions: thioester (1.0 equiv), Ni(dppp)Cl2 (10 mol%), Na2CO3 (1.5
equiv), dioxane (0.20 M), 160 °C, 15 h. bIsolated yields. cNi(PCy3)2Cl2.
d140 °C. See ESI for details.
Table
2
Substrate Scope: Ni-Catalyzed Decarbonylative
Thioetherificationa
Scheme
5
Site-Selective Cross-Coupling/Decarbonylative
Thioetherification
Yield
(%)
Entry
1
Thioester
1
Product
2
1a
2a 98
2c’ 85
2d’ 98
2
3
4
5
1p
1q
1r
Yamaguchi, Itami and co-workers recently reported a Ni-
catalyzed decarbonylative diaryl ether synthesis by C–O
cleavage.27 We were intrigued to find that the present
coupling proceeds in the presence of the sensitive aryl ester
linkage (Scheme 4), demonstrating high chemoselectivity of
the present method.
2e’ 91
2k’ 96
To further showcase the utility of this new
thioetherification, sequential orthogonal cross-couplings were
investigated (Scheme 5). This sequence highlights the potential
1s
This journal is © The Royal Society of Chemistry 2018
Chem. Commun., 2018, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 4
View Article Online
DOI: 10.1039/C8CC00271A
COMMUNICATION
Chemical Communications
Yorimitsu and A. Osuka, Chem. Eur. J., 2014, 20, 13146; (d)
M. Bhanuchandra, A. Baralle, S. Otsuka, K. Nogi, H. Yorimitsu
and A. Osuka, Org. Lett., 2016, 18, 2966.
of decarbonylative thioetherification to selectively generate
thioethers from readily available carboxylic acids.5,6,10
In conclusion, we have reported a general method for
decarbonylative thioetherification by C–S cleavage using a
commercially-available, user-friendly, inexpensive, air- and
moisture-stable nickel(II) precatalyst. The process provides a
synthetic entry to the biologically-relevant thioether functional
group exploiting abundant carboxylic acids as ultimate cross-
coupling precursors. In view of the synthetic utility of
thioethers and Ni(II) precatalysts, we anticipate that the
method will be of broad interest.28 Further studies on related
decarbonylative cross-coupling transformations are ongoing.
Rutgers University and the NSF (CAREER CHE-1650766) are
acknowledged for support.
10 (a) H. Ochiai, Y. Uetake, T. Niwa and T. Hosoya, Angew.
Chem. Int. Ed., 2017, 56, 2482; See, also: (b) Y. Uetake, T.
Niwa and T. Hosoya, Org. Lett., 2016, 18, 2758.
11 (a) J. A. Fernandez-Salas, A. J. Eberhart and D. J. Procter, J.
Am. Chem. Soc., 2016, 138, 790; (b) L. Shang, Y. Chang, F.
Luo, J. N. He, X. Huang, L. Zhang, L. Kong, K. Li and B. Peng, J.
Am. Chem. Soc., 2017, 139, 4211; (c) T. Yanagi, S. Otsuka, Y.
Kasuga, K. Fujimoto, K. Murakami, K. Nogi, H. Yorimitsu and
A. Otsuka, J. Am. Chem. Soc., 2016, 138, 14582; For excellent
study on metal-free fluoroalkylthiolation, see: (d) D. Zhu, Y.
Gu, L. Lu and Q. Shen, J. Am. Chem. Soc., 2015, 137, 10547.
12 (a) S. Z. Tasker, E. A. Standley and T. F. Jamison, Nature,
2014, 509, 299; (b) V. P. Ananikov, ACS Catal., 2015, 5, 1964.
13 For an excellent monograph on cross-couplings, see: (a) T. J.
Colacot, New Trends in Cross-Coupling, RSC, 2015; For
leading reviews, see: (b) P. G. Gildner and T. J. Colacot,
Organometallics, 2015, 34, 5497; (c) H. Li, C. C. C. Johansson-
Notes and references
1
For leading reviews on biological activity of thioethers, see:
(a) E. A. Ilardi, E. Vitaku and J. T. Njardson, J. Med. Chem.,
2014, 57, 2832; (b) M. Feng, B. Tang, S. H. Liang and X. Jiang,
Curr. Top. Med. Chem., 2016, 16, 1200.
Seechurn and T. J. Colacot, ACS Catal., 2012,
14 D. Zim, V. R. Lando, J. Dupont and A. L. Monteiro, Org. Lett.,
2001, , 3049.
2, 1147.
3
2
3
L. Brunton, B. Chabner and B. Knollman, Goodman and
Gilman’s The Pharmacological Basis of Therapeutics;
MacGraw-Hill, New York, 2010.
For excellent reviews on C–S bond formation, see: (a) C. C.
Eichman and J. P. Stambuli, Molecules, 2011, 16, 590; (b) J. P.
Stambuli, In New Trends in Cross-Coupling, T. J. Colacot, The
Royal Society of Chemistry, 2015, p. 254; (c) I. P. Beletskaya
and V. P. Ananikov, Chem. Rev., 2011, 111, 1596.
15 R. L. Jezorek, N. Zhang, P. Leowanawat, M. H. Bunner, N.
Gutsche, A. K. R. Pesti, J. T. Olsen and V. Percec, Org. Lett.,
2014, 16, 6326.
16 N. H. Park, G. Teverovskiy and S. L. Buchwald, Org. Lett.,
2014, 16, 220.
17 E. A. Stadley, S. J. Smith, P. Müller and T. F. Jamison,
Organometallics, 2014, 33, 2012.
18 J. D. Shields, E. E. Gray and A. G. Doyle, Org. Lett., 2015, 17
2166.
19 (a) J. Magano and S. Monfette, ACS Catal., 2015, 5, 3120; For
,
4
For recent selected examples of thioether synthesis, see: (a)
M. Jouffroy, C. B. Kelly and G. A. Molander, Org. Lett., 2016,
18, 876; (b) M. S. Oderinde, M. Frenette, D. W. Robbins, B.
a review on well-defined, bench-stable precatalysts, see: (b)
N. Hazari, P. R. Melvin and M. M. Beromi, Nat. Rev. Chem.,
2017, 1, 25.
Aquila and J. W. Johannes, J. Am. Chem. Soc., 2016, 138
,
1760; (c) B. Liu, C. H. Lim and G. M. Miyaka, J. Am. Chem.
Soc., 2017, 139, 13616; (d) C. Uyeda, Y. Tan, G. C. Fu and J. C.
Peters, J. Am. Chem. Soc., 2013, 135, 9548; (e) M. A.
Fernandez-Rodriguez, Q. Shen and J. F. Hartwig, J. Am. Chem.
Soc., 2006, 128, 2180; For a leading report on C–S
construction by C–H activation, see: (f) P. Saravanan and P.
Anbarasan, Org. Lett., 2014, 16, 848.
20 (a) G. Meng and M. Szostak, Angew. Chem. Int. Ed., 2015, 54
,
14518; (b) C. Liu, and G. Meng and M. Szostak, J. Org. Chem.,
2016, 81, 12023.
21 (a) S. Shi, G. Meng and M. Szostak, Angew. Chem. Int. Ed.,
2016, 55, 6959; (b) G. Meng and M. Szostak, Org. Lett., 2016,
18, 796; (c) G. Meng and M. Szostak, ACS Catal., 2017,
22 S. Shi and M. Szostak, Org. Lett., 2017, 19, 3095.
7, 7251.
5
For reviews, see: (a) R. Takise, K. Muto and J. Yamaguchi,
Chem. Soc. Rev., 2017, 46, 5864; (b) W. I. Dzik, P. P. Lange
and L. J. Gooßen, Chem. Sci., 2012, 3, 2671; For the seminal
23 C. Liu and M. Szostak, Angew. Chem. Int. Ed., 2017, 56, 12718.
24 For reviews, see: (a) G. Meng, S. Shi and M. Szostak, Synlett,
2016, 27, 2530; (b) C. Liu and M. Szostak, Chem. Eur. J., 2017,
23, 7157; For selected examples of decarbonylative cross-
coupling of amides, see: (c) A. Dey, S. Sasmai, K. Seth, G. K.
decarbonylative cross-coupling of aryl esters, see: (c) K.
Amaike, K. Muto, J. Yamaguchi and K. Itami, J. Am. Chem.
Soc., 2012, 134, 13573; For additional examples, see: (d) A.
Dermenci and G. Dong, Sci. China Chem., 2013, 56, 685.
Lahiri and D. Maiti, ACS Catal., 2017, 7, 433; (d) H. Yue, L.
6
7
For a comprehensive review, see: L. J. Goo
and K. Gooßen, Angew. Chem. Int. Ed., 2008, 47, 3100.
For reviews, see: (a) S. G. Modha, V. P. Mehta and E. V. Van
der Eycken, Chem. Soc. Rev., 2013, 42, 5042; (b) L. Wang, W.
He and Z. Yu, Chem. Soc. Rev., 2013, 42, 599; (c) S. R.
ßen, N. Rodriguez
Guo, H. H. Liao, Y. Cai, C. Zhu and M. Rueping, Angew. Chem.
Int. Ed., 2017, 56, 4282; (e) H. Yue, L. Guo, S. C. Lee, X. Liu
and M. Rueping, Angew. Chem. Int. Ed., 2017, 56, 3972; (f)
W. Srimontree, A. Chatupheeraphat, H. H. Liao and M.
Rueping, Org. Lett., 2017, 19, 3091; For selected examples of
decarbonylative cross-coupling of esters, see: (g) K. Muto, J.
Yamaguchi, D. G. Musaev and K. Itami, Nat. Commun., 2015,
Dubbaka and P. Vogel, Angew. Chem. Int. Ed., 2005, 44
7674; For selected relevant examples, see: (d) K. Osakada, T.
Yamamoto and A. Yamamoto, Tetrahedron Lett., 1987, 28
,
,
6
, 7508; (h) T. Okita, K. Kumazawa, R. Takise, K. Muto, K.
6321; (e) E. Wenkert and D. Chianelli, J. Chem. Soc., Chem.
Commun., 1991, 627; (f) Y. Minamo, H. Kuniyasu, K. Miyafuji
and N. Kambe, Chem. Commun., 2009, 3080.
Itami and J. Yamaguchi, Chem. Lett., 2017, 46, 218.
25 N. Ichiishi, C. A. Malapit, L. Wozniak and M. S. Sanford, Org.
Lett., 2018, 20, 44.
26 B. Cryer and M. Feldman, Am. J. Med., 1998, 104, 413.
27 R. Takise, R. Isshiki, K. Muto, K. Itami and J. Yamaguchi, J.
Am. Chem. Soc., 2017, 139, 3340.
28 We hypothesize that the mechanism involves selective
oxidative addition into the C–S bond (cf. C(aryl)–C(carbonyl)).
For precedent reports on C–S oxidative addition, see: refs.
7a–c, f and references cited therein.
8
9
(a) Z. Lian, B. N. Bhawal, P. Yu and B. Morandi, Science, 2017,
356, 1059; For a pertinent reversible process involving
decarbonylation, see: (b) X. Fang, B. Cacherat and B.
Morandi, Nat. Chem., 2017,
therein.
9, 1105 and references cited
(a) T. Sugahara, K. Murakami, H. Yorimitsu and A. Osuka,
Angew. Chem. Int. Ed., 2014, 53, 9329; (b) K. Gao, H.
Yorimitsu and A. Osuka, Angew. Chem. Int. Ed., 2016, 55,
4573; See, also: (c) S. Otsuka, D. Fujino, K. Murakami, H.
Decarbonylative Coupling via Selective C
O
−
S Cleavage
[Ni], -CO
S
R'
R'
S
Ar
Ar
4 | Chem. Commun., 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 2018
23 examples
ꢀ selective C−S cleavage ꢀ modular, air-stable Ni precatalyst
ꢀ carboxylic acid precursors ꢀ broad tolerance ꢀ high generality
Please do not adjust margins