CuI-catalyzed direct synthesis of diaryl thioethers from aryl boronic acids and arylsulfonyl chlorides

Article abstract of DOI:10.1002/aoc.5385

A CuI-catalyzed direct coupling of aryl boronic acids with arylsulfonyl chlorides for the preparation of diaryl thioethers was developed. The reaction is initiated by a PPh₃ reduction of the arylsulfonyl chloride, followed by a CuI-catalyzed C–S coupling with an aryl boronic acid. Various arylsulfonyl chlorides can directly serve as a sulfur source in this mild and efficient reaction giving the desired products in moderate to good yields. Moreover, this practical method has also been applied to the thioetherification of aryl iodides and acetylacetones.

Full text of DOI:10.1002/aoc.5385

Received: 20 September 2019
DOI: 10.1002/aoc.5385
Revised: 23 October 2019
Accepted: 24 October 2019
C O M M U N I C A T I O N
CuI-catalyzed direct synthesis of diaryl thioethers from aryl
boronic acids and arylsulfonyl chlorides
Keke Huang1 | Min Yang2 | Xiao-Jing Lai1 | Xin Hu2 | Guanyinsheng Qiu3
Jin-Biao Liu1
|
1School of Metallurgical and Chemical
A CuI-catalyzed direct coupling of aryl boronic acids with arylsulfonyl
chlorides for the preparation of diaryl thioethers was developed. The reaction
is initiated by a PPh3 reduction of the arylsulfonyl chloride, followed by a
CuI-catalyzed C–S coupling with an aryl boronic acid. Various arylsulfonyl
chlorides can directly serve as a sulfur source in this mild and efficient reaction
giving the desired products in moderate to good yields. Moreover, this practical
method has also been applied to the thioetherification of aryl iodides and
acetylacetones.
Engineering, Jiangxi University of Science
and Technology, 86 Hongqi Road,
Ganzhou, 341000, China
2Department of Forensic Science, Gannan
Medical University, 1 Yixueyuan Road,
Ganzhou, Jiangxi, 341000, China
3College of Biological, Chemical Science
and Engineering, Jiaxing University, 118
Jiahang Road, Jiaxing, 314001, China
Correspondence
Min Yang, Department of Forensic
Science, Gannan Medical University, 1
Yixueyuan Road, Ganzhou, Jiangxi
341000, China.
K E Y W O R D S
aryl boronic acid, arylsulfonyl chloride, Cu(I) catalysis, thioether
Email: jiayoudouchi@163.com
Guanyinsheng Qiu, College of Biological,
Chemical Science and Engineering,
Jiaxing University, 118 Jiahang Road,
Jiaxing 314001, China.
Email: qiuguanyinsheng@mail.zjxu.edu
Jin-Biao Liu, School of Metallurgical and
Chemical Engineering, Jiangxi University
of Science and Technology, 86 Hongqi
Road, Ganzhou 341000, China.
Email: liujinbiao@jxust.edu.cn
Funding information
Natural Science Foundation of China,
Grant/Award Number: 21762018,
21961014 and 21772067; technology
innovation outstanding young talents
program of Jiangxi province, Grant/Award
Number: 20192BCBL23009; Science and
Technology Project of Jiangxi Provincial
Education Department, Grant/Award
Number: 151357; program of Qingjiang
Excellent Young Talents of Jiangxi
University of Science and Technology,
Grant/Award Number:
JXUSTQJBJ2018003
Appl Organometal Chem. 2019;e5385.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5385

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HUANG ET AL.
1 | INTRODUCTION
Among these sulfur sources, arylsulfonyl chlorides
have emerged as promising thiol-free sulfur sources in
thioether synthesis due to their commercial availability
and price. In Vogel's work, arylsulfonyl chlorides have
been widely used as leaving groups in C–C bond forma-
tion.[19] In 2011, You et al. divulged the first metal-free
synthesis of di (hetero)aryl sulfides by directly using sul-
The thioether functionality is prevalent in numerous nat-
ural products and pharmaceutical compounds which pos-
sess significant biological activities (Figure 1).[1,2] The
structural modification of flavonoids via the introduction
of sulfur atoms, such as thio-flavopiridol analogs 1, has
attracted considerable attention due to their anti-
proliferative activity.[3,4] AZD4407 2 is being used as an
antiallergy/antiasthmatic agent for chronic obstructive
pulmonary diseases (COPD).[5] Nelfinavir 3 is employed
in the treatment of human immunodeficiency virus
(HIV) together with other medications.[6]
Due to the ubiquity of the diaryl thioether motif in
pharmaceuticals,[7] novel synthetic protocols have been
developed for their preparation[8] and recent attention
has focused on transition-metal catalyzed C (sp2)–S bond
formation.[9–12] The transition metal-catalyzed C-S cou-
pling of aryl halides or aryl boronic acids with thiols or
thiophenols is well developed, and has become one of the
most powerful protocols.[13] Recently, other alternative
approaches to diaryl thioethers using sulfenylating
fonyl chlorides as sulfur sources in the presence of PPh3
[20]
ꢀ
at 130 C.
Quite recently, Fu and co-workers reported
a CuI-catalyzed sulfenylation of organozinc reagents with
arylsulfonyl chlorides/PPh3.[21] Despite significant pro-
gress, the development of a new, direct and facile
sulfenylation of (hetero)arenes to afford diaryl thioethers
is still highly desired. In light of our efforts in developing
synthetic methodology under mild conditions towards
useful molecules,[22] we would like to avoid the use of
high temperatures and unstable organometallic reagents
for the synthesis of diaryl thioethers. Therefore, we have
developed an inexpensive procedure that utilizes
arylsulfonyl chlorides which can directly serve as sulfur
sources in the construction of diaryl thioethers with aryl
boronic acids under mild conditions (Scheme 1).
agents,
such
as
sulfenyl
quinone
halides,[16]
mono-O,S-acetals,[14]
N-thioaryl
At the outset of this investigation, optimization of the
reaction parameters was performed using p-
disulfides,[15]
phthalimides,[17] and thiols in combination with N-chlo-
rosuccinimide, Selectflfluor or iron (III) chloride have
also been developed.[18]
toluenesulfonyl
chloride
(TsCl)
1a
and
4-methoxyphenylboronic acid 2a as the model substrates,
the results of which are summarized in Table 1. We
FIGURE 1 Examples of bioactive thioethers
SCHEME 1 Arylsulfonyl chlorides
in C–C and C–S bond forming reactions

DIRECT THIOETHERIFICATION FROM ARYLSULFONYL CHLORIDE
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explored the sulfenylation of TsCl with 2a in the presence
of various catalysts such as CuI, CuBr, Cu2O, Cu (OAc)2,
and PdCl2 with PPh3, 1,10-phenanthroline (Phen) and
K2CO3 at 50 ꢀC under air (entries 1-5, Table 1). The reac-
tion of TsCl (1.0 equiv.) and 2a (1.5 equiv.) in the pres-
ence of PPh3 (2.0 equiv.), CuI (10%), Phen (10%) and
isolated yield (entry 1, Table 1). Alternatively, a trace
amount of product was detected in the model reaction
with PdCl2 (entry 5, Table 1). To our delight, when the
amount of CuI was reduced to 0.01 equiv, the yield of 3a
was increased to 77% (entry 7, Table 1). In order to try
and obtain better product yields, different reaction condi-
tions were screened. Firstly, the ratio of THF/DMSO was
investigated, and no significant increase in yield was
ꢀ
K2CO3 (3.0 equiv.) in THF/DMSO (V/V = 2: 1) at 50 C,
gave (4-methoxyphenyl)(p-tolyl)sulfane 3a in 71%
TABLE 1 Initial studies for the reaction of p-toluenesulfonyl chloride 1a with 4-methoxyphenylboronic acid 2aa
Entry
1
Base
Catalyst (%)
CuI (10)
CuBr (10)
Cu2O (10)
Cu (OAc)2 (10)
PdCl2 (10)
None
Ligand
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
Phen
None
Bpy
Solvent (V/V)
Temperature (ꢀC)
Yield b
71%
62%
40%
69%
trace
trace
77%
73%
69%
75%
70%
49%
56%
65%
trace
70%
trace
47%
trace
5%
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
None
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (4: 1)
THF: DMSO (1: 1)
dioxane: DMSO (2: 1)
THF: DMF (2: 1)
THF: MeCN (2: 1)
THF: MeOH (2: 1)
THF: CH2Cl2 (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
THF: DMSO (2: 1)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
100
RT
50
2
3
4
5
6
7
CuI (5)
8
CuI (5)
9
CuI (5)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
CuI (5)
CuI (5)
CuI (5)
CuI (5)
CuI (5)
CuI (5)
KOH
CuI (5)
Cs2CO3
t-BuONa
Et3N
CuI (5)
CuI (5)
CuI (5)
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
CuI (5)
CuI (5)
17%
trace
76%
68%
37%c
CuI (5)
proline
Phen
Phen
Phen
CuI (5)
CuI (5)
CuI (5)
Reaction conditions: a): TsCl (1a, 0.2 mmol), 4-methoxyphenylboronic acid (2a, 0.3 mmol), PPh3 (0.4 mmol), base (0.6 mmol), catalyst/ligand (catalyst:
ligand = 1: 1), solvent (3 ml), 4 hr, air; b): Isolated yields based on TsCl 1a. Phen = Phen, 2,20-bipyridine = Bpy. c) The loading of PPh3 was reduced to
0.2 mmol.

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HUANG ET AL.
TABLE 2 Reaction of arylsulfonyl chlorides with aryl boronic acids a
Reaction conditions: a) 1 (0.2 mmol), 2 (0.3 mmol), PPh3 (0.4 mmol), K2CO3 (0.6 mmol), CuI (5%), 1,10-phenanthroline (5%), THF (2 ml) and DMSO (1 ml),
50 ꢀC, 4 hr, air.

DIRECT THIOETHERIFICATION FROM ARYLSULFONYL CHLORIDE
5 of 9
SCHEME 2 Control experiments
observed by adjusting the ratio of solvents (entries 8 and
9, Table 1). Mixed solvent evaluation revealed that no
better yields were provided when using dioxane/DMSO,
THF/DMF, THF/MeCN, THF/MeOH, and THF/CH2Cl2
as the mixed-solvents (entries 10-15, Table 1). Next, sev-
eral bases such as KOH, Cs2CO3, t-BuONa and Et3N,
were explored but none of these bases provided better
results (entries 16-19, Table 1). Subsequently, several
other ligands were tested for this transformation (entries
20-22, Table 1). It was found that 2,20-bipyridine and pro-
line were not able to promote the reaction. Finally, the
effect of temperature was then examined; the results
groups were smoothly converted into diaryl thioethers
3a-h in good to excellent yields via reaction with
4-methoxyphenylboronic acid 2a. A variety of important
functional
groups,
including
nitro
(3c)
and
trifluoromethyl (3e) substituents were tolerated under
the optimized reaction conditions giving their
corresponding products in 49% and 60% yield, respec-
tively. In contrast, when using naphthalene-2-sulfonyl
chloride, the corresponding product 3h was obtained in
88% yield. The reaction of 4-methoxybenzene-1-sulfonyl
chloride with various aryl boronic acids was then investi-
gated. The results demonstrated that a series of func-
tional substituents, such as methyl, tert-butyl, carboxyl,
ꢀ
showed that temperatures above or below 50 C resulted
in lower yields of the desired product (entries 23 and
24, Table 1). When 1 equiv. of PPh3 was further
employed, the yield of the corresponding product was
dramatically decreased to 37% (entry 25, Table 1). The
best reaction conditions were found to be the following:
using CuI as the catalyst, Phen as the ligand, K2CO3 as
the base, PPh3 as the reducing agent, THF/DMSO as a
ꢀ
mixed solvent and conducting the reaction at 50 C. It
should be noted that a trace amount of 3a was obtained
under the model conditions in the absence of CuI (entry
6, Table 1) or K2CO3 (entry 15, Table 1). Additionally, no
desired product was obtained when the reaction was
conducted in the sole THF or DMSO solvent. Other
reductants (NaBH4, I2 or n-Bu4NI instead of PPh3)
and other oxidants (Ag2CO3 or H2O2 instead of O2) have
also been tested, but no better results were observed
(Table S1 in ESI).
The scope and generality of this CuI-catalyzed
sulfenylation of various aryl boronic acids with aromatic
sulfonyl chlorides/PPh3 was investigated using the opti-
mized conditions (Table 2). Arylsulfonyl chlorides 1 con-
taining either electron-donating or electron-withdrawing
FIGURE 2 Proposed mechanism

6 of 9
HUANG ET AL.
trifluoromethyl and chloro groups on the aromatic motif
of 2 were tolerated. Interestingly, compared with previ-
ous results, there was no obvious difference in yields
between 3a, 3b and 3e; however, the diaryl thioether 3g
was obtained in a lower yield of 57%. The influence of
steric hindrance on the reaction was not obvious, with
the bulky products 3K and 3I being obtained in yields of
65% and 58%, respectively. Unfortunately, when a
heteroaryl boronic acid was employed for the formation
of 3m, the desired product was obtained in only 18%
yield. To further explore the scope and the limitations of
the methodology, reactions of 4-chlorobenzene-1-sulfonyl
chloride or benzenesulfonyl chloride with different aryl
boronic acids were conducted (3n-3r). Among the results,
the corresponding products were obtained moderate
yields, except for 3o, which was prepared in a good yield
(72%). Unfortunately, when aliphatic sulfonyl chlorides
or boracic acids were used as the substrates, no antici-
pated products were observed.
To illustrate a possible mechanism for this transfor-
mation, several control experiments were conducted and
the results are summarized in Scheme 2. It was observed
that TsCl could be reduced by PPh3, forming the disulfide
4a in excellent yield. Based on the synthesis of the disul-
fide 4a, TsCl may serve as the starting material for fur-
ther sulfenylation with 4-methoxyphenylboronic acid 2a,
TABLE 3 Reaction of arylsulfonyl chlorides with aryl boronic acid pinacol ester or aryl iodides 8a
Entry
X
R'
R
Yield
27%
5%
1b
boronic acid pinacol ester
4-OMe
4-OMe
H
H
2
I
I
I
I
H
3
4-OMe
4-OMe
4-Me
trace
63%
61%
4
4-NO2
4-NO2
5
Reaction conditions: a) 1 (0.2 mmol), 8 (0.3 mmol), PPh3 (0.4 mmol), K2CO3 (0.6 mmol), CuI (5%), Pd (OAc)2 (5%), 1,10-phenanthroline (5%), THF (2 ml) and
DMSO (1 ml), 110 ꢀC, 10 hr, air; b) Without Pd (OAc)2.
SCHEME 3 Reactions of aryl sulfonyl chloride
with acetylacetone, ethyl acetoacetate and
β-naphthol

DIRECT THIOETHERIFICATION FROM ARYLSULFONYL CHLORIDE
7 of 9
affording 3a in 72% yield (Scheme 2a). Compared with
the standard conditions, a comparable yield was obtained
under an O2 atmosphere, but the product was obtained
in only 5% yield under a N2 atmosphere, showing the
important role of oxygen in this reaction (Scheme 2b). In
order to further investigate the reaction mechanism, two
commonly used radical scavengers (TEMPO and
1,1-diphenylethylene) were employed. In the presence of
the radical scavengers, 3a was obtained in yields of 60%
and 58%, respectively, and no other adducts were
detected by GC-MS (Scheme 2c and 2d). This may sug-
gest that this transformation does not occur via a radical
process.
In summary, we have developed an efficient and prac-
tical method for the preparation of diaryl thioethers via a
CuI-catalyzed direct coupling of aryl boronic acids with
arylsulfonyl chlorides. The reaction is initiated via initial
reduction of the arylsulfonyl chloride with PPh3 and sub-
sequent CuI-catalyzed C–S coupling with an aryl boronic
acid. Various arylsulfonyl chlorides were used as sulfur
sources for smooth coupling with aryl boronic acids; the
desired products were obtained in moderate to good
yields. Moreover, aryl iodides and acetylacetone could
also be employed in the reaction to afford the
corresponding thioethers. Work is ongoing to extend the
application of this methodology.
Thus, based on the above results and our previous
work, we have proposed a plausible mechanism for this
transformation (Figure 2).[23] Firstly, the arylsulfonyl
chloride is reduced by PPh3 to give the disulfide 4. After
cleavage by X-Cu(I)-L, Ar-S-Cu(I)L 5 is generated, which
is then oxidized by oxygen to give Ar-S-Cu (II)XL 6.[24]
Meanwhile, another half of ArSSAr 4 would react with
Ar0B (OH)2 2 forming the diaryl thioether 3. Tran-
smetalation of Ar0B (OH)2 2 occurs to generate Ar-S-Cu
(II)-Ar0L 7, which undergoes reductive elimination to
afford the corresponding diaryl thioether 3 and gave
Cu(0). Meanwhile, the oxygen in the air regenerated the
Cu(I)-catalyst.
ACKNOWLEDGMENTS
Financial supports from the Natural Science Foundation
of China (Nos: 21762018, 21961014 and 21772067), the
program of Qingjiang Excellent Young Talents of Jiangxi
University
of
Science
and
Technology
(JXUSTQJBJ2018003), Science and Technology Project of
Jiangxi Provincial Education Department (No. 151357),
and technology innovation outstanding young talents
program of Jiangxi province (20192BCBL23009) are
gratefully acknowledged.
ORCID
To further examine the scope of this method, aryl
boronic acid pinacol ester and aryl iodides were
employed in the reaction in place of aryl boronic acids
(Table 3). The use of a pinacol ester gave in only 27%
yield, even at a higher temperature (Entry 1, Table 3).
However, the reaction of aryl halides with arylsulfonyl
chlorides required additional palladium-catalyst. Only p-
nitrophenyliodide could be used as the aryl source for
smooth coupling with the arylsulfonyl chlorides (Entries
4 and 5, Table 3), and both p-methoxyphenyliodide and
phenyliodide were unreactive in the thioetherification
reaction (Entries 2 and 3, Table 3).
Additionally, acetylacetone, ethyl acetoacetate and
β-naphthol have been used as reaction substrates
(Scheme 3). For instance, treatment of ArSO2Cl with
acetylacetone 9a in the presence of CuI/Phen, PPh3, and
Et3N in THF/DMSO at 50 ꢀC for 10 hrs under air,
afforded the corresponding thioether 10a and 10b in 65%
and 43% yields, respectively (Scheme 3a). Acetylacetone
thioether was a versatile dual-functionalized synthon.[25]
However, ethyl acetoacetate is totally inert in this CuI-
catalyzed direct thioetherification reaction (Scheme 3b).
We have also investigated the reaction between TsCl and
β-naphthol under the mediation of molecular iodine, and
the corresponding thioether 10c was obtained in 72%
yield (Scheme 3c).
Jin-Biao Liu https://orcid.org/0000-0002-5038-6541
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Huang K, Yang M,
Lai X-J, Hu X, Qiu G, Liu J-B. CuI-catalyzed direct
synthesis of diaryl thioethers from aryl boronic
acids and arylsulfonyl chlorides. Appl Organometal
Chem. 2019;e5385. https://doi.org/10.1002/aoc.
5385