Copper-Catalyzed Three-Component One-Pot Synthesis of Aryl Sulfides with Sulfur Powder under Aqueous Conditions

Article abstract of DOI:10.1002/adsc.201600642

A copper-catalyzed three-component (arenes, iodohydrocarbon, and sulfur powder) synthesis of substituted aryl sulfides has been developed. Water is used as the green solvent in a simple and environmentally friendly procedure. Various functional groups attached to the substrates were well tolerated in this process to afford the corresponding products in moderate to good yields. (Figure presented.).

Full text of DOI:10.1002/adsc.201600642

UPDATES
DOI: 10.1002/adsc.201600642
Copper-Catalyzed Three-Component One-Pot Synthesis of Aryl
Sulfides with Sulfur Powder under Aqueous Conditions
Fuhong Xiao,a,* Shuqing Chen,a Cheng Li,a Huawen Huang,a and Guo-Jun Denga,*
a
Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry,
Xiangtan University, Xiangtan 411105, Peopleꢀs Republic of China
Fax : (+86)-0731-5829-2251; phone: (+86)-0731-5829-8601; e-mail: fhxiao@xtu.edu.cn or gjdeng@xtu.edu.cn
Received: June 20, 2016; Revised: September 5, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600642.
Abstract:
A
copper-catalyzed three-component
nomic route to construct the C–S bond by omitting
substrate pre-activation. Recently, we and others have
developed various approaches for C–H sulfuration
using sulfur powder as sulfur source,[11] whereby most
of the procedures described above were carried out in
organic solvents. From the perspective of green
chemistry, water is a desirable reaction medium be-
cause of its inexpensive, non-toxic nature and envi-
ronmental friendliness. As part of our continuing ef-
forts using water as an ideal solvent for C–H sulfeny-
lation,[12] herein we disclose a novel and environmen-
tally-friendly protocol for the synthesis of aryl sulfides
via C–H bond functionalization of arenes with iodo-
hydrocarbons and sulfur powder under aqueous con-
ditions (Scheme 1).
(arenes, iodohydrocarbon, and sulfur powder) syn-
thesis of substituted aryl sulfides has been devel-
oped. Water is used as the green solvent in a simple
and environmentally friendly procedure. Various
functional groups attached to the substrates were
well tolerated in this process to afford the corre-
sponding products in moderate to good yields.
Keywords: aryl sulfides; copper-catalyzed reaction;
sulfur powder; three-component reaction; water
Aryl sulfides are ubiquitous structural motifs found in
numerous pharmaceutically active compounds and
medicinally important natural products.[1] Therefore,
various methods for the formation of C–S bonds to
synthesize aryl sulfides have been developed. On the
basis of the sulfur source, there are two common
methods for the synthesis of aryl sulfides via cross-
coupling reactions. The first approach is based on the
transition metal-catalyzed cross-coupling reactions of
organic halides with organosulfur sources, and disul-
fides[2] or thiols[3] are the most popular reagents in
Scheme 1. Sulfenylation of arenes with iodohydrocarbons
and sulfur powder.
Our initial efforts were focused on searching for an
these reactions. Sulfuryl chloride,[4] sulfonylhydra- efficient catalytic system using 2-naphthol (1a), iodo-
zide[5] and sodium sulfinates[6] have also been reported benzene (2a), and sulfur powder as model substrates
as sources of the sulfide group. Another typical under aqueous conditions (Table 1). To our delight,
method is based on inorganic sulfur reagents, in an 80% yield of the desired product was obtained in
which sulfur powder (S8), which is abundant and the presence of 10 mol% Cu(OAc)2, 10 mol% 1,10-
smell-free in nature, has been extensively investigated phen and 1 equiv. of K2CO3 in H2O at 1208C for 24 h
for introducing sulfur atoms into organic molecules.[7] (entry 1). A variety of the other copper catalysts in-
Also, a variety of inorganic metal sulfides, such as cluding CuCl2, CuSO4, Cu(OTf)2, CuI was examined
Na2S,[8] K2S[9] and Na2SO3
used as a sulfur source.
have been successfully (entries 2–5), Among the catalysts screened,
Cu(OTf)2 showed the best efficiency to give the corre-
[10]
In recent years, the transition metal-catalyzed sponding product 3a in 89% yield (entry 5). The li-
direct sulfenylation of C–H bonds using inorganic gands play an important role in this kind of transfor-
sulfur as the sulfur source has attracted considerable mation. Among the various ligands screened, 1,10-
interest, since this strategy provides a more atom-eco- phen showed the best efficiency (entries 6–10). The
Adv. Synth. Catal. 0000, 000, 0 – 0
1
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
Table 1. Optimization of the reaction conditions.[a]
Table 2. Reaction of 2-naphthol with aryl halides.[a]
Entry
Catalyst
Ligand
Base
Yield [%][b]
Entry Aryl halide
No. Product Yield [%][b]
1
2
3
4
5
6
7
8
Cu(OAc)2
CuCl2
CuSO4
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
L1
TMEDA
L2
L3
Ph3P
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
1,10-phen
–
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
KOH
KHCO3
KO-t-Bu
Na2CO3
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
80
78
75
74
89
30
2
79
43
0
64
52
26
84
83
98
12
trace
86
10
trace
1
2
3
4
5
6
7
8
R=4-Me
R=4-OCH3
R=4-F
R=4-Cl
R=4-Br
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
2p
2q
2r
3ab
3ac
3ad
3ae
3af
3ag
3ah
3ai
75
80
75
90
73
40
80
70
68
78
77
66
71
85
83
77
80
90
83
73
80
CuI
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
R=4-I
R=4-CF3
R=4-NH2
R=4-NO2
R=4-CN
R=4-CHO
R=4-COCH3
R=4-COOCH3
R=4-Ph
R=2-Me
R=2-OMe
R=2-NH2
R=3-Me
R=3-OMe
R=3-NO2
9
9
3aj
3ak
3al
10
11
12
13
14
15
16[c]
17
18
19[d]
20[f]
21[g]
10
11
12
13
14
15
16
17
18
19
20
21
3am
3an
3ao
3ap
3aq
3ar
3as
3at
2s
2t
2u
3au
3av
–
1-iodonaphthalene 2v
[a]
Conditions: 1a (0.5 mmol), 2a (0.75 mmol), sulfur
(1.0 mmol), catalyst (10 mol%), ligand (10 mol%), base
(0.5 mmol), H2O (1.0 mL), 1208C, 24 h, under air; L1=
2,2-bipyridine, L2=4,5-diazafluoren-9-one, L3=1,10-
phenanthroline-5,6-dione.
GC yield.
K2CO3 (0.75 mmol).
Under argon.
Bromobenzene instead of iodobenzene.
Chlorobenzene instead of iodobenzene.
[a]
Conditions: 1a (0.5 mmol),
(1.0 mmol), copper triflate (10 mol%), 1,10-Phen
(10 mol%), K2CO3 (150 mol%), in H2O (1 mL), 1208C,
air, 24 h.
2
(0.75 mmol), sulfur
[b]
Isolated yield.
[b]
[c]
[d]
[e]
[f]
sponding products in reasonable yields (entries 1 and
2). Halogen substituents such as trifluoromethyl,
fluoro, chloro, bromo and iodo were all well tolerated
under the optimized reaction conditions (entries 3–7),
reaction was less efficient when other base were and the desired product 3ae was isolated in 90% yield
tested (entries 11–15). The yield can be improved to when 1-chloro-4-iodobenzene (2e) was used (entry 4).
98% by increasing the amount of K2CO3 to 1.5 equiv. It should be noted that 1,4-diiodobenzene was also
(entry 16). Copper triflate as catalyst and 1,10-phen as able to couple with 1a to give the desired monosul-
ligand are both necessary, and very low yields were
ACHTUNGTRENfNUNG uration product (entry 6) in 40% yield, and the
obtained when the reaction was carried out in the ab- carbon-iodine bond may be cleavable. Therefore,
sence either one (entries 17 and 18). The yield did not there are many by-products generated. Moreover, an
change when the reaction was carried out under active amino group substituent on iodobenzene was
argon (entry 19). Unfortunately, Bromobenzene and well tolerated, and the desired product (3ai) was ob-
chlorobenzene are not suitable for this transformation tained in 70% yield (entry 8). Other substrates bear-
under the optimal conditions (entries 20 and 21). It ing electron-withdrawing groups such as nitro, cyano,
should be noted that no 2-phenoxynaphthalene by- aldehyde, acetyl and aliphatic groups remained effec-
product was observed with the present system.
tive and gave the corresponding arylsulfonamides in
With the optimized conditions in hand, a variety of good yields (entries 9–13). There seems to be little
aryl iodides was examined under the optimized reac- effect of the substituent position (ortho or meta) of
tion conditions to explore the scope of the substrates, the benzene ring on the reaction yield. For example,
as summarized in Table 2. Methyl- and methoxyiodo- when the methyl was located in an ortho (2p) and in
benzenes reacted smoothly with 1a to give the corre- a meta (2s) position on the benzene ring, the corre-
Adv. Synth. Catal. 0000, 000, 0 – 0
2
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
sponding products 3ap and 3as were obtained in 83% bromoethyl)benzene also worked with 1a to afford
and 90% yields, respectively (entry 15, entry 18). Sim- the corresponding sulfide product 3ada in 35% yield
ilarly, when a methoxy groups was located at the (entry 8).
ortho (2q) and meta (2t) position on the benzene ring,
To further examine the scope and limitations of the
the corresponding products 3ap and 3as were ob- sulfenylation reaction, we tested various arene deriva-
tained in 77% and 83% yields, respectively (entry 16, tives for this kind of reaction (Table 4). 2-Naphthols
entry 19). When 2-iodoaniline (2r) and 1-iodo-3-nitro- with a bromo group at C-6 or C-7 both smoothly cou-
benzene (2u) were employed, the corresponding pled with 2a and gave the desired products 3ba and
products 3ar and 3au were obtained in 80% and 73% 3ca in 60% and 68% yields, respectively. Besides 7-
yields, respectively (entry 17, entry 20). In addition, bromonaphthalen-2-ol which reacted smoothly with
more bulky substrates such as iodonaphthalene also iodobenzene, other substrates bearing functional
reacted with 1a and gave the product 3av in 80% groups such as 2c, 2e, and 2l gave the aryl sulfides
yield (entry 21).
3cc, 3ce and 3cl, respectively, in moderate to good
To our delight, besides iodobenzenes, this reaction yields. Promising results from naphthalen-2-ol moti-
system could also be applied to the direct sulfenyla- vated us to further extend this new protocol to naph-
tion of heterocyclic halogen derivatives and alkyl hal- thalen-2-amine derivatives. It is noteworthy that the
ides with 1a (Table 3). Moderate to good yields were compounds 1d and 1e were tolerated in this reaction
achieved when the heteroaromatic iodine-containing and afforded the corresponding products 3da and 3ea
compounds such as 3-iodopyridine (2w), 3-iodo-2-me- in 41% and 60% yields, respectively. We further
thoxypyridine (2x) and 5-iodopyridin-2-amine (2y) tested this method with naphthalen-1-ol under the op-
were used (entries 1–3). When 2-iodothiophene (2z)
was used, the desired product 3az was observed,
Table 4. Substrate scope.[a]
albeit in 35% yield (entry 4). Furthermore, notewor-
thy is that an alkyl iodide coupled with 1a to give the
corresponding sulfide product (entries 5–7), and (2-
Table 3. Sulfenylation of 2-naphthol with halides.[a]
<
Entry
1
Aryl halide
No.
Product
Yield [%][b]
82
2w
3aw
2
2x
3ax
80
3
4
2y
2z
3ay
3az
68
35
5
6
2aa
2ab
3aaa
3aba
55
48
7
2ac
2ad
3aca
3ada
21
35
8
[a]
[a]
Conditions: 1a (0.5 mmol),
2
(0.75 mmol), sulfur
Conditions:
1
(0.5 mmol),
2
(0.75 mmol), sulfur
(1.0 mmol), copper triflate (10 mol%), 1,10-Phen
(1.0 mmol), copper triflate (10 mol%), 1,10-Phen
(10 mol%), K2CO3 (150 mol%), in H2O (1 mL), 1208C,
(10 mol%), K2CO3 (150 mol%), in H2O (1 mL), 1208C,
air, 24 h.
Isolated yield.
air, 24 h.
Isolated yield.
[b]
[b]
Adv. Synth. Catal. 0000, 000, 0 – 0
3
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
timized conditions. Encouragingly, the reactions fur-
Control experiments were carried out to gain pre-
nished the corresponding 4-(phenylthio)naphthalen-1- liminary insights into the mechanism of the catalytic
ol 3fa in 50% yield. On the basis of results obtained procedure. The product 3ab could be gained in 92%
in the case of electron-rich arenes, we have further yield when catalyzed by 10 mol% of p-tolylSCu
extended this strategy to 2-phenylimidazo[1,2-a]pyri- (Scheme 3a), however, a stoichiometric reaction of p-
dine derivatives (1g–1i). We carried out the reactions tolylSCu with 2-naphthol did not proceed under an
of 2-phenylimidazo[1,2-a]pyridine derivatives with 2a N2 or an O2 atmosphere (Scheme 3b). These results
under the aforementioned conditions. It was found indicate that p-tolylSCu would not be an intermediate
that the 2-phenylimidazo[1,2-a]pyridine derivatives but be an active catalyst in the catalytic cycle. It is in-
were well tolerated in this transformation to give the teresting that the 1-(p-tolylthio)naphthalen-2-ol (3ab)
corresponding products in good yields (3ga, 3ha, 3ia). was obtained in 40% and the by-product 1,2-di-p-tolyl
To our surprise, the naphtho[1’,2’:5,6]-[1,4]oxathi- disulfide (2bb) was obtained in 35% when 2 equiv. of
ACHTUNGTRENNUNG
chloro-3-iodopyridine as the substrate (Scheme 2).
during the procedure and elemental S could serve as
an oxidant. That also is in agreement with the obser-
vation that the reaction could proceed smoothly
under an argon atmosphere (Table 1, entry 16).
According to our above control experiments and
related references, a proposed mechanism is illustrat-
ed in Scheme 4. It is known that sulfur could undergo
a disproportionation reaction in the presence of
a base to produce sulfide anion and sulfite.[13] The
first step of the catalytic cycle would be an oxidative
addition of copper with iodobenzene to afford com-
plex B. Then B undergoes ligand exchange with S2À
followed by reductive elimination and further ligand
exchange of XÀ with PhSÀ species to produce the
complex C, which is the catalytically active species
and proceeds through a 2nd oxidative addition/ligand
exchange/reductive elimination sequence to regener-
ate the complex C and molecular PhSÀ. Then the S8-
Scheme 2. Cyclic reaction of 2-naphthol.
Scheme 3. Control experiments.
Adv. Synth. Catal. 0000, 000, 0 – 0
4
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
gel, petroleum ether/ethyl acetate=20:1) to give 3aa as
white solid; yield: 108 mg (86%).
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21372187, 21502160, 21572194),
Hunan Provincial Natural Science Foundation of China
(16JJ3112), the Scientific Research Fund of Hunan Provin-
cial Education Department (15C1311, YB2016B024), and the
China Postdoctoral Science Foundation Funded Project
(2015M572257).
References
[1] a) F. Bernardi, I. G. Csizmadia, A. Mangini, Organic
Sulfur Chemistry. Theoretical and Experimental Advan-
ces, Elsevier, Amsterdam, 1985, vol. 19; b) P. Kielbasin-
ski, Phosphorus Sulfur Silicon Relat. Elem. 2011, 186,
1104; c) Sulfur Compounds: Advances in Research and
Application, (Ed.: A. Q. Acton), Scholarly Editions,
Atlanta, GA, 2012.
[2] a) H. Liu, X. Jiang, Chem. Asian J. 2013, 8, 2546;
b) J. F. Hartwig, Acc. Chem. Res. 2008, 41, 1534; c) T.
Kondo, T. Mitsudo, Chem. Rev. 2000, 100, 3205; d) S. V.
Ley, A. W. Thomas, Angew. Chem. 2003, 115, 5558;
Angew. Chem. Int. Ed. 2003, 42, 5400.
[3] a) Y. Yang, W. B. Dong, Y. S. Guo, R. M. Rioux, Green
Chem. 2013, 15, 3170; b) Z. Jiang, J. She, X. F. Lin,
Adv. Synth. Catal. 2009, 351, 2558; c) D. W. Ma, Q. Cai,
Acc. Chem. Res. 2008, 41, 1450; d) W. Y. Wu, J. C.
Wang, F. Y. Tsai, Green Chem. 2009, 11, 326; e) L.
Rout, T. K. Sen, T. Punniyamurthy, Angew. Chem.
2007, 119, 5679; Angew. Chem. Int. Ed. 2007, 46, 5583;
f) S. K. R. Parumala, R. K. Peddinti, Green Chem.
2015, 17, 4068.
Scheme 4. Proposed catalytic cycle.
initiated oxidation affords the complex E,[14] which
could undergo reductive elimination to generate the
1,2-diphenyl disulfide. This could also rationalize why
small amounts of disulfides were detected in the reac-
tion. Subsuquently, the electrophilic metallation of
1 with E occurs to give intermediate F. Finally, the in-
termediate F undergoes reductive elimination to gen-
erate the sulfenylation product and the catalyst C.
In summary, we have developed a simple and effi-
cient method for preparing aryl sulfides from arenes,
iodohydrocarbon, and sulfur powder under aqueous
conditions. Copper triflate acted as an efficient cata-
lyst for this kind of transformation. Halogen, nitro,
cyano, aldehyde, acetyl and amino functional groups
were well tolerated under the optimized reaction con-
ditions. This method affords an efficient alternative
approach for the synthesis of biologically important
heterodiaryl sulfides from sulfur powder.
´
[4] a) X. D. Zhao, E. Dimitrijevic, V. M. Dong, J. Am.
Chem. Soc. 2009, 131, 3466; b) O. Saidi, J. Marafie,
A. E. W. Ledger, P. M. Liu, M. F. Mahon, G. Kociok-
Kçhn, M. K. Whittlesey, C. G. Frost, J. Am. Chem. Soc.
2011, 133, 19298; c) H. W. Liang, K. Jiang, W. Ding, Y.
Yuan, L. Shuai, Y. C. Chen, Y. Wei, Chem. Commun.
2015, 51, 16928; d) H. J. Qiao, S. Y. Sun, F. Yang, Y.
Zhu, W. G. Zhu, Y. X. Dong, Y. S. Wu, X. T. Kong, L.
Jiang, Y. J. Wu, Org. Lett. 2015, 17, 6086; e) J. Wei,
J. X. Jiang, X. S. Xiao, D. G. Lin, Y. F. Deng, Z. F. Ke,
H. F. Jiang, W. Zeng, J. Org. Chem. 2016, 81, 946.
´
[5] a) X. D. Zhao, E. Dimitrijevic, V. M. Dong, J. Am.
Experimental Section
Chem. Soc. 2009, 131, 3466; b) Y. F. Xu, P. Liu, S. L. Li,
P. P. Sun, J. Org. Chem. 2015, 80, 1269; c) D. Zhang,
X. L. Cui, Q. Q. Zhang, Y. J. Wu, J. Org. Chem. 2015,
80, 1517; d) J. D. Liu, L. Yu, S. B. Zhuang, Q. W. Gui,
X. Chen, W. D. Wang, Z. Tan, Chem. Commun. 2015,
51, 6418; e) W. H. Rao, B. F. Shi, Org. Lett. 2015, 17,
2784; f) H. W. Liang, K. Jiang, W. Ding, Y. Yuan, L.
Shuai, Y. C. Chen, Y. Wei, Chem. Commun. 2015, 51,
16928; g) O. Saidi, J. Marafie, A. E. W. Ledger, P. M.
Liu, M. F. Mahon, G. Kociok-Kçhn, M. K. Whittlesey,
C. G. Frost, J. Am. Chem. Soc. 2011, 133, 19298.
General Procedure
A 10-mL oven-dried reaction vessel was charged with naph-
thalen-2-ol (1a, 72 mg, 0.5 mmol), sulfur (32 mg, 1.0 mmol),
Cu(OTf)2 (18 mg, 0.05 mmol), 1,10-phen (9 mg, 0.05 mmol),
K2CO3 (103.7 mg, 0.75 mmol), iodobenzene (2a, 83.5 mL,
0.75 mmol) and H2O (1.0 mL) under air. The resulting solu-
tion was stirred at 1208C for 24 h. After cooling to room
temperature the volatiles were removed under vacuum and
the residue was purified by column chromatography (silica
Adv. Synth. Catal. 0000, 000, 0 – 0
5
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
[6] a) X. D. Tang, L. B. Huang, Y. L. Xu, J. D. Yang, W. Q.
Wu, H. F. Jiang, Angew. Chem. 2014, 126, 4289; Angew.
Chem. Int. Ed. 2014, 53, 4205; b) X. S. Wu, Y. Chen,
M. B. Li, M. G. Zhou, S. K. Tian, J. Am. Chem. Soc.
2012, 134, 14694; c) W. H. Rao, B. F. Shi, Org. Lett.
2015, 17, 2784; d) S. Handa, J. C. Fennewald, B. H. Lip-
shutz, Angew. Chem. 2014, 126, 3500; Angew. Chem.
Int. Ed. 2014, 53, 3432.
[7] a) M. E. Helton, P. Chen, P. P. Paul, Z. Tyeklꢂr, R. D.
Sommer, L. N. Zakharov, A. L. Rheingold, E. I. Solo-
mon, K. D. Karlin, J. Am. Chem. Soc. 2003, 125, 1160;
b) C. Chen, Y. Xie, L. L. Chu, R. W. Wang, X. G.
Zhang, F. L. Qing, Angew. Chem. 2012, 124, 2542;
Angew. Chem. Int. Ed. 2012, 51, 2492; c) T. B. Nguyen,
L. Ermolenko, P. Retailleau, A. Al-Mourabit, Angew.
Chem. 2014, 126, 14028; Angew. Chem. Int. Ed. 2014,
53, 13808; d) G. T. Zhang, H. Yi, H. Chen, C. L. Bian,
C. Liu, A. W. Lei, Org. Lett. 2014, 16, 6156; e) Y. W.
Jiang, Y. X. Qin, S. W. Xie, X. J. Zhang, J. H. Dong,
D. W. Ma, Org. Lett. 2009, 11, 5250; f) J. Xu, L. L.
Zhang, X. Q. Li, Y. Z. Gao, G. Tang, Y. F. Zhao, Org.
Lett. 2016, 18, 1266.
11, 2473; c) L. L. Sun, C. L. Deng, R. Y. Tang, X. G.
Zhang, J. Org. Chem. 2011, 76, 7546; d) C. L. Li, X. G.
Zhang, R. Y. Tang, P. Zhong, J. H. Li, J. Org. Chem.
2010, 75, 7037.
[9] W. You, X. Yan, Q. Liao, C. Xi, Org. Lett. 2010, 12,
3930.
[10] a) Z. Qian, H. Liu, X. Xiao, Y. Fu, J. Wei, Y. Li, X.
Jiang, Org. Lett. 2013, 15, 2594; b) Y. M. Li, J. H. Pu,
X. F. Jiang, Org. Lett. 2014, 16, 2692; c) J. T. Reeves, K.
Camara, Z. S. Han, Y. Xu, H. Lee, C. A. Busacca, C. H.
Senanayake, Org. Lett. 2014, 16, 1196; d) Z. J. Qiao,
J. P. Wei, X. F. Jiang, Org. Lett. 2014, 16, 1212.
[11] a) Y. F. Liao, Y. Peng, H. R. Qi, G. J. Deng, H. Gong,
C. J. Li, Chem. Commun. 2015, 51, 1031; b) J. J. Chen,
G. Z. Li, Y. J. Xie, Y. F. Liao, F. H. Xiao, G. J. Deng,
Org. Lett. 2015, 17, 5870; c) T. Guntreddi, R. Vanjari,
K. N. Singh, Org. Lett. 2015, 17, 976; d) T. B. Nguyen,
K. Pasturaud, L. Ermolenko, A. Al-Mourabit, Org.
Lett. 2015, 17, 2562.
[12] F. H. Xiao, S. Q. Chen, J. X. Tian, H. W. Huang, Y. J.
Liu, G. J. Deng, Green Chem. 2016, 18, 1538.
[13] Y. Jiang, Y. Qin, S. Xie, X. Zhang, J. Dong, D. Ma,
Org. Lett. 2009, 11, 5250.
[8] a) D. Ma, S. Xie, P. Xue, X. Zhang, J. Dong, Y. Jiang,
Angew. Chem. 2009, 121, 4286; Angew. Chem. Int. Ed.
2009, 48, 4222; b) T. Kashiki, S. Shinamura, M. Kohara,
K. Takimiya, M. Ikeda, H. Kuwabara, Org. Lett. 2009,
[14] J. T. Yu, H. Guo, Y. Yi, H. Fei, Y. Jiang, Adv. Synth.
Catal. 2014, 356, 749.
Adv. Synth. Catal. 0000, 000, 0 – 0
6
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
Copper-Catalyzed Three-Component One-Pot Synthesis of
Aryl Sulfides with Sulfur Powder under Aqueous
Conditions
7
Adv. Synth. Catal. 2016, 358, 1 – 7
Fuhong Xiao,* Shuqing Chen, Cheng Li, Huawen Huang,
Guo-Jun Deng*
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!