A highly efficient heterogeneous copper-catalyzed Chan-Lam coupling between thiols and arylboronic acids leading to diaryl sulfides under mild conditions

Article abstract of DOI:10.1016/j.tet.2016.04.063

The heterogeneous Chan-Lam coupling reaction between thiols and arylboronic acids was achieved in EtOH at room temperature in the presence of 5 mol % of MCM-41-immobilized 1,10-phenanthroline-copper(II) complex [MCM-41-1,10-Phen-CuSO₄] with n-Bu₄NOH (40% aq) as base under O₂ atmosphere, yielding a variety of unsymmetrical diaryl sulfides in good to excellent yields under mild and green conditions. The new heterogeneous copper complex can easily be prepared by a simple procedure from commercially readily available and inexpensive reagents, and recovered by a simple filtration of the reaction solution and recycled for at least eight times without significant loss of catalytic activity.

Full text of DOI:10.1016/j.tet.2016.04.063

Tetrahedron xxx (2016) 1e9
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
A highly efficient heterogeneous copper-catalyzed Chan-Lam
coupling between thiols and arylboronic acids leading to diaryl
sulfides under mild conditions
,
a
a,
Yang Lin a, Mingzhong Cai b , Zhiqiang Fang , Hong Zhao
*
*
a School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, PR China
b College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The heterogeneous Chan-Lam coupling reaction between thiols and arylboronic acids was achieved in
EtOH at room temperature in the presence of 5 mol % of MCM-41-immobilized 1,10-phenanthroline-
copper(II) complex [MCM-41-1,10-Phen-CuSO4] with n-Bu4NOH (40% aq) as base under O2 atmosphere,
yielding a variety of unsymmetrical diaryl sulfides in good to excellent yields under mild and green
conditions. The new heterogeneous copper complex can easily be prepared by a simple procedure from
commercially readily available and inexpensive reagents, and recovered by a simple filtration of the
reaction solution and recycled for at least eight times without significant loss of catalytic activity.
Ó 2016 Elsevier Ltd. All rights reserved.
Received 27 February 2016
Received in revised form 21 April 2016
Accepted 22 April 2016
Available online xxx
Keywords:
Chan-Lam coupling
Supported copper catalyst
Diaryl sulfide
MCM-41
Heterogeneous catalysis
1. Introduction
commercially available boronic acids and derivatives and the
mildness of the reaction conditions.11 Cu-catalyzed cross-couplings
Diaryl sulfides are important scaffolds in natural products,1
material chemistry,2 and pharmaceuticals.3 They have been
widely applied as intermediates in organic synthesis4 and as li-
gands in transition-metal-catalyzed reactions.5 Transition-metal-
catalyzed carboneheteroatom cross-coupling reactions are a pow-
erful tool for the preparations of fine chemicals, pharmaceuticals,
and materials.6 In the past two decades, there have been numerous
advances in the synthesis of diaryl sulfides via the carbonesulfur
couplings of aryl halides with thiols or disulfides mediated by
transition metals such as palladium,7 copper,8 nickel,9 and iron.10
However, the high cost of palladium catalysts restricts their appli-
cations in large-scale preparation and the scope of copper and
other metal catalyst systems are suitable only for aryl iodides/
bromides or triflates. Moreover, these methods often require ele-
vated temperatures. It is thus desirable to develop a milder (room
temperature), eco-friendly, efficient and practical catalyst system
for the CeS bond formation reactions.
of amines12 and phenols13 with organoboronic acids and de-
rivatives have made great progress in the past decade. Since Guy
et al. reported the first CeS cross-coupling reaction of arylboronic
acids with electron-rich alkyl thiols in the presence of Cu(OAc)2,14
copper-catalyzed Chan-Lam coupling reactions of arylboronic
acids with thiols or diaryl disulfides have also attracted consider-
able interest,15 providing a novel, efficient and practical route to
diaryl sulfides.
However, the majority of reported Chan-Lam coupling systems,
in particular the systems that use homogeneous copper catalysts,
have been susceptible to contamination by the cytotoxic copper
ions, which restricts the application of such systems in electronics
and biomedicine. Although both chromatographic purification of
the crude product and washing the crude product with ethyl-
enediaminetetraacetic acid (EDTA) or ammonia are acceptable
methods, they are scavenger-, energy-, and time-consuming pro-
cedures. The heterogenization of Chan-Lam coupling catalysts ap-
pears to be a logical solution; the use of supported catalysts could
result in easy removal, recovery, and recyclability of the copper
catalyst, thereby, minimizing copper contamination of the desired
isolated products and wastes derived from reaction workup. Until
now, several supports such as polymers,16 silica,17 zeolites,18 acti-
vated carbon,19 alumina,20 carbon nanotubes,21 and magnetic
The Chan-Lam coupling reaction has emerged as a highly effi-
cient and valuable alternative to traditional methods for the con-
struction of carboneheteroatom bonds due to the wide variety of
* Corresponding authors. E-mail addresses: mzcai@jxnu.edu.cn (M. Cai),
zhaohong1001@sina.com (H. Zhao).
http://dx.doi.org/10.1016/j.tet.2016.04.063
0040-4020/Ó 2016 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

2
Y. Lin et al. / Tetrahedron xxx (2016) 1e9
nanoparticles22 have been employed for immobilization of copper
catalysts. In 2004, Chiang et al. reported the first heterogeneous
CeN and CeO cross-coupling reactions between boronic acids and
N-containing substrates or phenols by using a modified Wang
resin-supported copper complex as catalyst.16a To the best of our
knowledge, there is no report of heterogeneous copper-catalyzed
Chan-Lam coupling reaction of between thiols and arylboronic
acids thus far.
The discovery of mesoporous MCM-41 materials has provided
a new possible candidate for a solid support for immobilizing ho-
mogeneous catalysts and given an enormous stimulus to research
in heterogeneous catalysis.23 The hexagonally ordered material
MCM-41 has ultrahigh surface area, large and defined pore size, big
pore volume and rich silanol groups in the inner walls.24 To date,
some functionalized MCM-41-immobilized palladium, rhodium,
molybdenum, and copper complexes have been prepared and
successfully applied in organic synthesis.25 In continuation of our
efforts to develop economical and eco-friendly synthetic pathways
for organic transformations,25gej herein we wish to report the first
toluene at room temperature for 24 h to generate the 1,10-
phenanthroline-functionalized MCM-41 [MCM-41-1,10-Phen]. The
latter was then reacted with CuSO4 in acetone under reflux for 24 h
to afford the MCM-41-immobilized 1,10-phenanthroline-copper(II)
complex [MCM-41-1,10-Phen-CuSO4] as a light green powder, the
copper content of the catalyst was found to be 0.82 mmol/g
according to the ICP-AES measurements.
X-ray powder diffraction (XRD) patterns of the parent MCM-41
and the modified material MCM-41-1,10-Phen-CuSO4 are displayed
in Fig. 1. Small angle X-ray diffraction of the parent MCM-41 gave
the peaks corresponding to hexagonally ordered mesoporous
phases. For MCM-41-1,10-Phen-CuSO4, the (100) reflection of
MCM-41 with decreased intensity was remained after functionali-
zation, while the (110) and (200) reflections became weak and
diffuse, which should be attributed to contrast matching between
the silicate framework and organic moieties which are located in-
side the channels of MCM-41. These results indicate that the
structure of the mesoporous material remains intact through the
grafting procedure.
synthesis
of
1,10-phenanthroline-functionalized
MCM-41-
In our initial screening experiments, the cross-coupling of
phenylboronic acid with thiophenol was chosen as the model re-
action to optimize the reaction conditions, which include base,
solvent, and reaction time and the results are summarized in Table
1. At first, the base effect was examined by using 5 mol % of MCM-
41-1,10-Phen-CuSO4 as catalyst in MeOH (Table 1, entries 1e14). It is
evident that only low yields were obtained when traditional in-
organic bases such as Cs2CO3, K2CO3, Na2CO3, K3PO4, NaOH, NaOtBu
and KOtBu were used. When Cs2CO3 was employed as base in neat
immobilized copper(II) complex [MCM-41-1,10-Phen-CuSO4] and
its successful application to Chan-Lam coupling reaction between
thiols and arylboronic acids (Scheme 1). The new heterogeneous
copper catalyst exhibits high catalytic activity in EtOH at room
temperature with n-Bu4NOH (40% aq) as base and can easily be
recovered by a simple filtration of the reaction solution, and its
catalytic efficiency remains unaltered even after recycling eight
times.
Scheme 1. Heterogeneous copper-catalyzed Chan-Lam coupling between thiols and arylboronic acids.
2. Results and discussion
water, only trace of the desired product was detected since the
catalyst could not be swollen in neat water (entry 9). However,
when tetra-n-butylammonium hydroxide (n-Bu4NOH) was
employed, the yield increased to 44% (entry 10). To our delight, the
yield could be further improved by changing the ratio of n-Bu4NOH
(40% aq) to MeOH. It was found that the use of a 1:1 mixture of n-
Bu4NOH (40% aq) and MeOH afford the best result, and any other
ratios gave lower yields (entries 10e14). Our next studies focused
The new MCM-41-immobilized 1,10-phenanthroline-copper(II)
complex [MCM-41-1,10-Phen-CuSO4] was easily prepared accord-
ing to the procedure summarized in Scheme 2. Firstly, the meso-
porous material MCM-4126 was treated with 1-(1,10-
phenanthrolin-5-yl)-3-(3-(triethoxysilyl)propyl)urea27 in toluene
under reflux for 24 h, followed by the silylation with Me3SiCl in
Scheme 2. Preparation of MCM-41-1,10-Phen-CuSO4.
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

Y. Lin et al. / Tetrahedron xxx (2016) 1e9
3
performed under air atmosphere (entry 23). Thus, the optimized
reaction conditions for this transformation are the MCM-41-1,10-
Phen-CuSO4 (5 mol %) in EtOH (0.5 mL) with n-Bu4NOH (40% aq,
0.5 mL) as base at room temperature under O2 atmosphere for 8 h
(entry 19).
With this promising result in hand, we started to examine the
scope and limitation of this heterogeneous copper-catalyzed Chan-
Lam coupling reaction between thiols and arylboronic acids under
the optimized conditions. Firstly, reactions of phenylboronic acid
(1a) with various thiols were examined and the results are sum-
marized in Table 2. The reactions of a variety of substituted thio-
phenols bearing both electron-donating and electron-withdrawing
groups with phenylboronic acid (1a) proceeded smoothly in EtOH
at room temperature under O2 atmosphere, leading to the desired
products 3be3g in good to high yields (72e89%) within 8 h. The
results indicated that the electronic effect of substituents on the
benzene ring has limited influence on this heterogeneous copper-
catalyzed Chan-Lam coupling reaction. The sterically hindered 2-
methylthiophenol was also coupled with PhB(OH)2 effectively to
give a high yield of cross-coupled product 3h. Unfortunately, ali-
phatic thiols such as butane-1-thiol and phenylmethanethiol were
not suitable for this heterogeneous catalytic system.
Fig. 1. XRD patterns of MCM-41 (1) and MCM-41-1,10-Phen-CuSO4 (2).
Encouraged by the above results, we next turned our attention
to examine reactions of a variety of arylboronic acids with various
thiols under the optimized conditions and the results are outlined
in Table 3. As shown in Table 3, all reactions of both electron-rich
and electron-poor arylboronic acids with thiophenol proceeded
smoothly to furnish the corresponding cross-coupled products 3b
and 3ie3n in good to excellent yields (63e91%). Interestingly, 4-
vinylphenylboronic acid gave the desired product 3m in excellent
yield and no addition of thiophenol to the double bond was ob-
served. The coupling reaction appears to be insensitive to the
on the effect of solvent on the model reaction. Among the solvents
examined, dioxane, THF and EtOH afforded good yields and EtOH
was found to be the best choice, giving an 83% yield of diphenyl
sulfide within 8 h (entry 19). While other solvents such as DMSO
and DMF were substantially less effective (entries 15 and 18). Re-
ducing the amount of the catalyst to 2 mol % resulted in a slightly
lower 80% yield (entry 21). Increasing the amount of the catalyst
could shorten the reaction time, but did not improve the yield of
the desired product (entry 22). It is noteworthy that, the desired
product was obtained in only 58% yield when the reaction was
Table 1
Cross-coupling between phenylboronic acid and thiophenol in different conditionsa
Entry
Base
Solvent
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
Cs2CO3 (5 equiv)
Cs2CO3 (3 equiv)
K2CO3 (5 equiv)
Na2CO3 (5 equiv)
MeOH (2.0 mL)
MeOH (2.0 mL)
MeOH (2.0 mL)
MeOH (2.0 mL)
MeOH (2.0 mL)
MeOH (2.0 mL)
MeOH (2.0 mL)
MeOH (2.0 mL)
H2O (2.0 mL)
MeOH (1.5 mL)
MeOH (0.4 mL)
MeOH (0.6 mL)
MeOH (0.5 mL)
none
DMSO (0.5 mL)
Dioxane (0.5 mL)
THF (0.5 mL)
DMF (0.5 mL)
EtOH (0.5 mL)
EtOH (0.5 mL)
EtOH (0.5 mL)
EtOH (0.5 mL)
EtOH (0.5 mL)
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
8
32
13
29
26
21
18
23
25
trace
44
49
59
75
trace
37
65
69
55
83
84
80
82
58
K3PO4 (5 equiv)
NaOH (5 equiv)
NaOtBu (5 equiv)
KOtBu (5 equiv)
9
Cs2CO3 (5 equiv)
10
11
12
13
14
15
16
17
18
19
20
21c
22d
23e
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.6 mL)
n-Bu4NOH (40% aq, 0.4 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 1.0 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
n-Bu4NOH (40% aq, 0.5 mL)
14
16
5
24
a
All reactions were performed using 0.5 mmol of PhB(OH)2, 0.75 mmol of PhSH, 5 mol % of MCM-41-1,10-Phen-CuSO4 at room temperature under O2 atmosphere.
Isolated yield.
2 mol % of copper catalyst was used.
10 mol % of copper catalyst was used.
Under air atmosphere.
b
c
d
e
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

4
Y. Lin et al. / Tetrahedron xxx (2016) 1e9
Table 2
Reaction of phenylboronic acid with various thiols catalyzed by MCM-41-1,10-Phen-CuSO4a,b
Table 3
Reaction of arylboronic acids with thiols catalyzed by MCM-41-1,10-Phen-CuSO4a,b
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

Y. Lin et al. / Tetrahedron xxx (2016) 1e9
5
electronic properties of substituents on the benzene ring. The re-
actions of sterically hindered 2-chlorophenylboronic acid and 2-
trifluoromethylphenylboronic acid with thiophenol could give the
desired coupled products 3o and 3p in good yields. We were
pleased to observe that heteroarylboronic acids such as pyridin-3-
ylboronic acid and bulky naphthalen-1-ylboronic acid also afforded
the corresponding products 3q and 3r in good yields. However, the
reaction of isoquinolin-4-ylboronic acid with thiophenol gave the
desired product 3s in only 61% yield. In addition, the reactions of
arylboronic acids with substituted thiophenols with various sub-
stituents, regardless of their electronic properties and substitution
positions, all afforded the expected products 3te3z in good to ex-
cellent yields (69e92%) under the optimized conditions. It is
noteworthy that, sterically hindered 2-chlorophenylboronic acid
could be coupled effectively with sterically hindered o-toluenethiol
to give the desired product 3a’ in 68% yield at higher temperature
(60 ꢀC) and on a longer time (48 h). A wide range of functional
These results demonstrated that the prepared catalyst was stable
during the reactions and the observed catalysis was intrinsically
heterogeneous.
This heterogeneous copper-catalyzed Chan-Lam coupling re-
action of thiols with arylboronic acids may proceed through
a mechanism analogous to that proposed for the CuSO4/1,10-
phenanthroline catalytic system (Scheme 3).15l Firstly, the trans-
metalation of the aryl group from boron to copper produces MCM-
41-immobilized 1,10-phenanthroline-CuIIeAr1 intermediate A.
Then there would be two paths to complete the catalytic cycle. It is
well known that aromatic thiols are easily oxidized to diaryl
disulfides by Cu(II) under O2 atmosphere. The reaction of in-
termediate A with diaryl disulfides affords intermediate B and the
desired product 3.15f Then intermediate
B undergoes trans-
metalation with arylboronic acid 1 to produce intermediate C (path
A). The intermediate A may react with Ar2Sꢁ derived from Ar2SH
and n-Bu4NOH to directly form intermediate C (path B). Finally,
Scheme 3. Proposed mechanism.
groups such as methyl, methoxy, vinyl, cyano, nitro, chloro, bromo,
fluoro, and trifluoromethyl were well tolerated in the heteroge-
neous Cu-catalyzed Chan-Lam coupling reaction. The method
provides a quite general route for the synthesis of unsymmetrical
diaryl sulfides having various functionalities under mild and green
conditions.
To determine whether the observed catalysis was due to the
heterogeneous catalyst MCM-41-1,10-Phen-CuSO4 or to a leached
copper species in solution, the reaction of phenylboronic acid (1a)
with thiophenol (2a) was carried out until an approximately 50%
conversion of 1a was reached. Then the MCM-41-1,10-Phen-CuSO4
catalyst was removed from the reaction mixture by filtration and
the filtrate was again stirred at room temperature under O2 at-
mosphere for 6 h. In this case, no significant increase in conversion
was observed, indicating that leached copper species from the
supported catalyst (if any) are not responsible for the observed
activity. It was confirmed by ICP-AES analysis that no copper spe-
cies could be detected in the solution (below the detection limit).
intermediate C undergoes reductive elimination to produce the
desired product 3 and Cu(0) species intermediate D, which is then
oxidized by O2 to regenerate the MCM-41-1,10-Phen-CuSO4.
For the practical application of a heterogeneous transition-
metal catalyst system its stability and reusability are important
factors. We next examined the recyclability of the MCM-41-1,10-
Phen-CuSO4 complex by using cross-coupling reaction between
4-fluorothiophenol (0.75 mmol) and 4-chlorophenylboronic acid
(0.5 mmol) with n-Bu4NOH (40% aq) (0.5 mL) as base in EtOH
(0.5 mL) in the presence of 5 mol % of MCM-41-1,10-Phen-CuSO4 at
room temperature under O2 atmosphere for 8 h. After carrying out
the reaction, the catalyst was separated by simple filtration and
washed with distilled water and EtOH. After being air-dried, it can
be reused directly without further purification. The recovered
copper catalyst was used in the next run, and almost consistent
activity was observed for eight consecutive cycles (Fig. 2). In ad-
dition, copper leaching in the supported catalyst was also de-
termined. The copper content of the catalyst was found by ICP
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

6
Y. Lin et al. / Tetrahedron xxx (2016) 1e9
(100 MHz) were recorded on a Bruker Avance 400 MHz spectro-
meter in CDCl3 as solvent. Copper content was determined with
inductively coupled plasma atom emission Atomscan16 (ICP-AES,
TJA Corporation). X-ray powder diffraction was obtained on Dam-
axegA (Rigaku). Microanalyses were measured by using a Yanaco
MT-3 CHN microelemental analyzer.
4.2. Preparation of the 1,10-phenanthroline-functionalized
MCM-41 (MCM-41-1,10-Phen)
A solution of 1.47 g of 1-(1,10-phenanthrolin-5-yl)-3-(3-(trie-
thoxysilyl)propyl)urea in 9 mL of dry chloroform was added to
a suspension of 1.10 g of the MCM-41 in 90 mL of dry toluene. The
mixture was stirred for 24 h at 110 ꢀC under Ar. Then the solid was
filtered and washed by CHCl3 (2ꢂ20 mL), and dried in vacuum at
160 ꢀC for 5 h. The product was then soaked in a solution of 4.2 g of
Me3SiCl in 80 mL of dry toluene at room temperature under stirring
for 24 h. Then the solid was filtered, washed with acetone
(3ꢂ20 mL) and diethyl ether (3ꢂ20 mL), and dried in vacuum at
120 ꢀC for 5 h to obtain 1.53 g of hybrid material MCM-41-1,10-
Phen. The nitrogen content was found to be 3.66 mmol/g by ele-
mental analysis.
Fig. 2. Recycle of the MCM-41-1,10-Phen-CuSO4 catalyst.
analysis to be 0.81 mmol/g after eight consecutive runs, only 1% of
copper had been lost from the MCM-41 support. The excellent re-
usability of the catalyst should be attributed to the chelating action
of 1,10-phenanthroline ligand on copper and the mesoporous
structure of the MCM-41 support. The result is important from
industrial and environmental points of view. The high catalytic
activity and excellent reusability of the MCM-41-1,10-Phen-CuSO4
complex make it a highly attractive heterogeneous copper catalyst
for the parallel solution phase synthesis of diverse libraries of
compounds.
4.3. Preparation of the MCM-41-1,10-Phen-CuSO4 catalyst
In a small Schlenk tube, 1.2 g of the above-functionalized MCM-
41 material (MCM-41-1,10-Phen) was mixed with 0.18 g (1.1 mmol)
of CuSO4 in 20 mL of dry acetone. The mixture was refluxed for 24 h
under an argon atmosphere. The solid product was filtered by
suction, washed with acetone, distilled water and acetone succes-
sively and dried at 70 ꢀC/26.7 Pa under Ar for 5 h to give 1.32 g of
a light green copper complex [MCM-41-1,10-Phen-CuSO4]. The ni-
trogen and copper content were found to be 3.42 mmol/g and
0.82 mmol/g, respectively.
3. Conclusion
In summary, we have successfully developed a novel, highly
efficient and practical method for the synthesis of diaryl sulfides
through Chan-Lam coupling reaction of arylboronic acids with
thiols by using an MCM-41-immobilized 1,10-phenanthroline-
copper(II) complex [MCM-41-1,10-Phen-CuSO4] as catalyst and n-
Bu4NOH (40% aq) as base in EtOH at room temperature under O2
atmosphere. The reactions generated a variety of unsymmetrical
diaryl sulfides in good to excellent yields under mild and green
conditions and were applicable to various arylboronic acids and
thiols. The new heterogeneous copper catalyst can be easily pre-
pared by a simple procedure from commercially available and in-
expensive reagents and recycled for at least eight times without
significant loss of catalytic activity. The use of recyclable copper
catalyst along with mild and environment-friendly reaction con-
ditions will make this methodology a powerful complement to the
traditional CeS coupling reactions.
4.4. General procedure for the heterogeneous copper-
catalyzed cross-coupling reaction of arylboronic acids with
thiols
An oven-dried Schlenk tuble equipped with a magnetic stirring
bar was charged with MCM-41-1,10-Phen-CuSO4 (30 mg,
0.025 mmol), arylboronic acid (0.5 mmol), and thiol (0.75 mmol) (if
solid). The tube was evacuated and filled with oxygen. Then EtOH
(0.5 mL) was added by a syringe under a counter flow of oxygen.
After stirring for 5 min, n-Bu4NOH (40% aq) (0.5 mL) was added by
a syringe under a counter flow of oxygen. Next, thiol (0.75 mmol) (if
liquid) was added by a syringe under a counter flow of oxygen. The
resulting reaction mixture was stirred at 25 ꢀC for 8e24 h. The
reaction mixture was then diluted with EtOAc (20 mL), and filtered.
The MCM-41-1,10-Phen-CuSO4 complex was washed with distilled
water (2ꢂ5 mL) and EtOH (3ꢂ5 mL), and reused in the next run. The
filtrate was washed with water (2ꢂ5 mL) and dried over anhydrous
magnesium sulfate. The solvent was removed under reduced
pressure and the residue was purified by flash column chroma-
tography on silica gel.
4. Experimental
4.1. Physical measurements and materials
All chemicals were reagent grade and used as purchased. All
solvents were dried and distilled before use. Mesoporous material
MCM-41 was prepared by standard protocol.26 1-(1,10-
Phenanthrolin-5-yl)-3-(3-(triethoxysilyl)propyl)urea was pre-
pared via the addition of 5-amino-1,10-phenanthroline to 3-(trie-
thoxysilyl)propyl isocyanate according to a literature procedure.27
The products were purified by flash chromatography on silica gel.
Mixture of EtOAc and hexane was generally used as eluent. All
cross-coupling products were characterized by comparison of their
spectra and physical data with authentic samples. 1H NMR spectra
were recorded on a Bruker Avance 400 MHz spectrometer with
TMS as an internal standard in CDCl3 as solvent. 13C NMR spectra
4.4.1. Diphenyl sulfide (3a). Colorless oil.7h 1H NMR (400 MHz,
CDCl3):
131.1, 129.2, 127.1.
d
¼7.35e7.19 (m, 10H). 13C NMR (100 MHz, CDCl3):
¼135.8,
d
4.4.2. 4-Methylphenyl phenyl sulfide (3b). Colorless oil.7h 1H NMR
(400 MHz, CDCl3):
¼7.29 (d, J¼7.6 Hz, 2H), 7.25e7.16 (m, 5H), 7.12
d
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

Y. Lin et al. / Tetrahedron xxx (2016) 1e9
7
(d, J¼7.6 Hz, 2H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3):
d¼137.6,
CDCl3):
127.5, 127.2, 127.0.
d
¼140.3, 140.0, 135.7, 134.9, 131.3, 131.2, 129.3, 128.9, 127.9,
137.2, 132.3, 131.3, 130.1, 129.8, 129.1, 126.4, 21.2.
4.4.3. 4-Methoxyphenyl phenyl sulfide (3c). Colorless oil.7h 1H NMR
4.4.15. 2-Chlorophenyl phenyl sulfide (3o). Colorless oil.29 1H NMR
(400 MHz, CDCl3):
d
¼7.41 (d, J¼8.4 Hz, 2H), 7.23 (t, J¼7.2 Hz, 2H),
(400 MHz, CDCl3):
d
¼7.46e7.33 (m, 6H), 7.14e7.07 (m, 2H),
7.18e7.10 (m, 3H), 6.89 (d, J¼8.8 Hz, 2H), 3.81 (s, 3H). 13C NMR
6.98e6.94 (m, 1H). 13C NMR (100 MHz, CDCl3):
d¼136.6, 133.3,
(100 MHz, CDCl3):
115.0, 55.4.
d
¼159.9, 138.6, 135.4, 128.9, 128.3, 125.8, 124.4,
133.0, 132.8, 130.2, 129.8, 129.6, 128.3, 127.3, 127.2.
4.4.16. Phenyl 2-trifluoromethylphenyl sulfide (3p). Colorless oil.8c
4.4.4. 4-Isopropylphenyl phenyl sulfide (3d). Colorless oil.28 1H NMR
1H NMR (400 MHz, CDCl3):
d
¼7.69e7.66 (m, 1H), 7.43e7.23 (m,
(400 MHz, CDCl3):
d¼7.31 (d, J¼8.0 Hz, 2H), 7.29e7.19 (m, 5H), 7.18
7H), 7.18 (d, J¼7.6 Hz, 1H). 13C NMR (100 MHz, CDCl3):
¼136.8,
d
(d, J¼8.0 Hz, 2H), 2.88 (q, J¼6.8 Hz, 1H), 1.24 (d, J¼7.2 Hz, 6H). 13
C
133.9, 133.1, 132.4, 132.1, 129.6, 128.2, 126.7 (q, J¼5.6 Hz), 126.3,
NMR (100 MHz, CDCl3):
127.5, 126.5, 33.8, 23.9.
d
¼148.4, 136.9, 132.0, 131.8, 130.1, 129.1,
125.2, 122.5.
4.4.17. (3-Phenylthio)pyridine (3q). Pale yellow oil.32 1H NMR
4.4.5. 4-Fluorophenyl phenyl sulfide (3e). Colorless oil.7h 1H NMR
(400 MHz, CDCl3):
(m, 1H), 7.40e7.28 (m, 5H), 7.23e7.18 (m, 1H); 13C NMR (100 MHz,
CDCl3):
¼151.0, 147.9, 137.9, 133.9, 133.7, 131.8, 129.5, 127.9, 123.9.
d
¼8.56 (s, 1H), 8.46 (d, J¼4.0 Hz, 1H), 7.61e7.56
(400 MHz, CDCl3):
d
¼7.40e7.35 (m, 2H), 7.28e7.21 (m, 5H), 7.02 (t,
J¼8.6 Hz, 2H). 13C NMR (100 MHz, CDCl3):
d
¼162.4 (d,
d
1JCꢁF¼246.1 Hz), 136.6, 134.1 (d, JCꢁF¼8.2 Hz), 130.0, 129.2, 126.8,
116.4 (d, 2JCꢁF¼21.9 Hz).
3
4.4.18. (1-Phenylthio)naphthalene (3r). Colorless oil.7h 1H NMR
(400 MHz, CDCl3):
¼8.40e8.33 (m, 1H), 7.87e7.79 (m, 2H), 7.65 (d,
J¼7.2 Hz, 1H), 7.51e7.47 (m, 2H), 7.40 (t, J¼7.6 Hz, 1H), 7.22e7.12 (m,
5H). 13C NMR (100 MHz, CDCl3):
d
4.4.6. 4-Chlorophenyl phenyl sulfide (3f). Colorless oil.7h 1H NMR
(400 MHz, CDCl3):
d
¼7.34 (d, J¼8.0 Hz, 2H), 7.30 (d, J¼8.0 Hz, 2H),
d
¼137.0, 134.3, 133.7, 132.6, 131.3,
7.28e7.21 (m, 5H). 13C NMR (100 MHz, CDCl3):
d
¼135.2,134.7,133.0,
129.3, 129.1, 129.0, 128.6, 127.0, 126.5, 126.2, 125.9, 125.7.
132.0, 131.4, 129.4, 129.3, 127.5.
4.4.19. (4-Phenylthio)isoquinoline (3s). Colorless oil. 1H NMR
4.4.7. 4-Bromophenyl phenyl sulfide (3g). Colorless oil.29 1H NMR
(400 MHz, CDCl3):
8.01 (d, J¼8.0 Hz, 1H), 7.73e7.69 (m, 1H), 7.67e7.61 (m, 1H),
7.23e7.13 (m, 5H). 13C NMR (100 MHz, CDCl3):
d
¼9.23 (s, 1H), 8.66 (s, 1H), 8.27 (d, J¼8.8 Hz, 1H),
(400 MHz, CDCl3):
d
¼7.31 (d, J¼8.4 Hz, 2H), 7.28e7.17 (m, 5H),
7.09e7.06 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
¼135.5, 133.0,
d¼153.3,148.0,136.4,
132.3, 132.1, 131.6, 129.4, 127.6, 120.9.
135.7,131.4,130.9,129.2,129.0,128.9,128.2,127.9, 126.6,124.7. Anal.
Calcd for C15H11NS: C, 75.91; H, 4.67; N, 5.90; S, 13.51. Found: C,
75.65; H, 4.52; N, 5.63; S, 13.33.
4.4.8. 2-Methylphenyl phenyl sulfide (3h). Colorless oil.7h 1H NMR
(400 MHz, CDCl3):
d
¼7.29 (d, J¼7.6 Hz, 1H), 7.25e7.18 (m, 7H), 7.13
(t, J¼7.4 Hz, 1H), 2.37 (s, 3H). 13C NMR (100 MHz, CDCl3):
d
¼140.0,
4.4.20. 4-Isopropylphenyl 4-methoxyphenyl sulfide (3t). Colorless
136.2, 133.8, 133.1, 130.6, 129.7, 129.1, 127.9, 126.7, 126.4, 20.6.
oil. 1H NMR (400 MHz, CDCl3):
d
¼7.37 (d, J¼8.0 Hz, 2H), 7.14 (d,
J¼8.0 Hz, 2H), 7.10 (d, J¼8.0 Hz, 2H), 6.87 (d, J¼7.6 Hz, 2H), 3.80 (s,
4.4.9. 3,5-Dimethylphenyl phenyl sulfide (3i). Colorless oil.8b 1H
3H), 2.88e2.80 (m, 1H), 1.21 (d, J¼6.8 Hz, 6H). 13C NMR (100 MHz,
NMR (400 MHz, CDCl3):
d
¼7.32e7.17 (m, 5H), 6.99 (s, 2H), 6.88 (s,
CDCl3):
d
¼159.6, 147.1, 134.8, 134.6, 129.2, 127.2, 125.5, 114.9, 55.4,
1H), 2.26 (s, 6H). 13C NMR (100 MHz, CDCl3):
130.6, 129.2, 129.1, 126.7, 21.2.
d
¼138.9, 136.5, 134.8,
33.7, 23.9. Anal. Calcd for C16H18OS: C, 74.38; H, 7.02; S, 12.41.
Found: C, 74.15; H, 6.77; S, 12.33.
4.4.10. 4-(Phenylthio)benzonitrile (3j). Pale yellow oil.15l 1H NMR
4.4.21. 4-Fluorophenyl 4-methoxyphenyl sulfide (3u). Colorless
(400 MHz, CDCl3):
(100 MHz, CDCl3):
118.9, 108.7.
d
¼7.55e7.41 (m, 7H), 7.19e7.13 (m, 2H). 13C NMR
oil.33 1H NMR (400 MHz, CDCl3):
d
¼7.35 (d, J¼8.0 Hz, 2H), 7.23e7.16
d
¼145.8, 134.6, 132.4, 130.0, 129.5, 127.4, 127.3,
(m, 2H), 6.94 (t, J¼8.2 Hz, 2H), 6.86 (d, J¼8.0 Hz, 2H), 3.79 (s, 3H). 13
C
1
NMR (100 MHz, CDCl3):
d
¼161.7 (d, JCꢁF¼244.5 Hz), 159.7, 134.5,
4
3
133.2 (d, JCꢁF¼3.3 Hz), 131.2 (d, JCꢁF¼7.9 Hz), 125.4, 116.1 (d,
4.4.11. 4-Trifluoromethylphenyl phenyl sulfide (3k). Colorless oil.7h
1H NMR (400 MHz, CDCl3):
¼7.51e7.44 (m, 4H), 7.41e7.35 (m,
3H), 7.27e7.20 (m, 2H). 13C NMR (100 MHz, CDCl3):
2JCꢁF¼21.8 Hz), 115.0, 55.4.
d
d
¼142.9, 133.5,
4.4.22. 4-Chlorophenyl 4-fluorophenyl sulfide (3v). Colorless oil.15l
132.6, 129.7, 128.7, 128.3, 127.6, 125.8 (q, J¼3.7 Hz), 122.8.
1H NMR (400 MHz, CDCl3):
d
¼7.38e7.34 (m, 2H), 7.23 (d,
J¼8.4 Hz, 2H), 7.15 (d, J¼8.8 Hz, 2H), 7.02 (t, J¼8.6 Hz, 2H). 13C NMR
4.4.12. 3-Nitrophenyl phenyl sulfide (3l). Pale yellow oil.30 1H NMR
(100 MHz, CDCl3):
d
¼162.6 (d, JCꢁF¼247.0 Hz), 135.4, 134.4 (d,
1
4
(400 MHz, CDCl3):
1H), 7.49e7.45 (m, 3H), 7.41e7.37 (m, 4H). 13C NMR (100 MHz,
CDCl3):
d
¼8.02 (t, J¼2.0 Hz, 1H), 7.98 (d, J¼8.0 Hz,
3JCꢁF¼8.2 Hz), 132.8, 131.0, 129.7 (d, JCꢁF¼3.4 Hz), 129.3, 116.6 (d,
2JCꢁF¼21.9 Hz).
d
¼148.7, 140.6, 134.3, 133.5, 129.9, 129.7, 129.0, 128.8,
123.1, 120.9.
4.4.23. 2-Methylphenyl 3-nitrophenyl sulfide (3w). Pale yellow oil.
1H NMR (400 MHz, CDCl3):
d
¼7.90e7.85 (m, 1H), 7.81 (t, J¼1.8 Hz,
1H), 7.40 (d, J¼7.6 Hz, 1H), 7.32e7.24 (m, 4H), 7.18e7.14 (m, 1H),
2.29 (s, 3H). 13C NMR (100 MHz, CDCl3):
4.4.13. Phenyl 4-vinylphenyl sulfide (3m). Colorless oil.31 1H NMR
(400 MHz, CDCl3):
d
¼7.36e7.24 (m, 9H), 6.68 (dd, J¼17.6, 10.8 Hz,
d
¼148.7, 141.9, 140.7, 135.5,
1H), 5.74 (d, J¼17.2 Hz, 1H), 5.25 (d, J¼10.8 Hz, 1H). 13C NMR
134.5, 133.0, 131.3, 129.9, 129.7, 127.4, 121.9, 120.4, 20.7. Anal. Calcd
for C13H11NO2S: C, 63.65; H, 4.52; N, 5.71; S, 13.07. Found: C, 63.42;
H, 4.27; N, 5.49; S, 12.89.
(100 MHz, CDCl3):
127.1, 127.0, 114.2.
d
¼136.5, 136.1, 135.8, 135.2, 131.1, 131.0, 129.2,
4.4.14. 4-Phenylphenyl
phenyl
sulfide
(3n). White
solid,
4.4.24. 2-Chlorophenyl 4-methoxyphenyl sulfide (3x). Colorless
mp 69e70 ꢀC (ref.15l mp 70e71 ꢀC). 1H NMR (400 MHz, CDCl3):
oil.34 1H NMR (400 MHz, CDCl3):
d¼7.46 (d, J¼8.8 Hz, 2H), 7.35e7.31
d
¼7.60e7.50 (m, 4H), 7.45e7.22 (m, 10H). 13C NMR (100 MHz,
(m, 1H), 7.07e7.01 (m, 2H), 6.96e6.94 (m, 2H), 6.72e6.69 (m, 1H),
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

8
Y. Lin et al. / Tetrahedron xxx (2016) 1e9
4005e4008; (h) Mao, J.; Jia, T.; Frensch, G.; Walsh, P. J. Org. Lett. 2014, 16,
3.84 (s, 3H). 13C NMR (100 MHz, CDCl3):
129.5, 127.5, 127.1, 126.1, 121.6, 115.4, 55.4.
d
¼160.6, 138.8, 137.0, 131.0,
5304e5307.
8. For selected examples, see (a) Kwong, F. Y.; Buchwald, S. L. Org. Lett. 2002, 4,
3517e3520; (b) Bates, C. G.; Gujadhur, R. K.; Venkataraman, D. Org. Lett. 2002, 4,
2803e2806; (c) Taniguchi, N.; Onami, T. J. Org. Chem. 2004, 69, 915e920; (d)
Kumar, S.; Engman, L. J. Org. Chem. 2006, 71, 5400e5403; (e) Chen, Y.-J.; Chen,
H.-H. Org. Lett. 2006, 8, 5609e5612; (f) Lv, X.; Bao, W.-L. J. Org. Chem. 2007, 72,
3863e3867; (g) Rout, L.; Sen, T. K.; Punniyamurthy, T. Angew. Chem., Int. Ed.
2007, 46, 5583e5586; (h) Sperotto, E.; van Klink, G. P. M.; de Vries, J. G.; van
Koten, G. J. Org. Chem. 2008, 73, 5625e5628; (i) Chen, C.-K.; Chen, Y.-W.; Lin, C.-
H.; Lin, H.-P.; Lee, C.-F. Chem. Commun. 2010, 282e284; (j) Huang, Y.-B.; Yang,
C.-T.; Yi, J.; Deng, X.-J.; Fu, Y.; Liu, L. J. Org. Chem. 2011, 76, 800e810; (k) Kao, H.-
L.; Lee, C.-F. Org. Lett. 2011, 13, 5204e5207; (l) Sun, L.-L.; Deng, C.-L.; Tang, R.-Y.;
Zhang, X.-G. J. Org. Chem. 2011, 76, 7546e7550; (m) Chen, C.; Weng, Z.; Hartwig,
J. F. Organometallics 2012, 31, 8031e8037; (n) Uyeda, C.; Tan, Y.; Fu, G. C.; Peters,
J. C. J. Am. Chem. Soc. 2013, 135, 9548e9552.
9. (a) Taniguchi, N. J. Org. Chem. 2004, 69, 6904e6906; (b) Baldovino-Pantaleon,
O.; Hernandez-Ortega, S.; Morales-Morales, D. Adv. Synth. Catal. 2006, 348,
236e242; (c) Zhang, Y.-G.; Ngeow, K. C.; Ying, J. Y. Org. Lett. 2007, 9,
3495e3498; (d) Jammi, S.; Barua, P.; Rout, L.; Saha, P.; Punniyamurthy, T. Tet-
rahedron Lett. 2008, 49, 1484e1487.
10. (a) Wu, J.-R.; Lin, C.-H.; Lee, C.-F. Chem. Commun. 2009, 4450e4452; (b) Wu,
W.-Y.; Wang, J.-C.; Tsai, F.-Y. Green Chem. 2009, 11, 326e329.
11. Qiao, J.-X.; Lam, P. Y. S. Synthesis 2011, 829e856.
12. For selected examples, see: (a) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.;
Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron Lett. 1998, 39, 2941e2944;
(b) Collman, J. P.; Zhong, M. Org. Lett. 2000, 2, 1233e1236; (c) Antilla, J. C.;
Buchwald, S. L. Org. Lett. 2001, 3, 2077e2080; (d) Quach, T. D.; Batey, R. A. Org.
Lett. 2003, 5, 4397e4400; (e) Lan, J.-B.; Chen, L.; Yu, X.-Q.; You, J.-S.; Xie, R.-G.
Chem. Commun. 2004, 188e189; (f) Moessner, C.; Bolm, C. Org. Lett. 2005, 7,
2667e2670; (g) Kantam, M. L.; Venkanna, G. T.; Sridhar, C.; Sreedhar, B.;
Choudary, B. M. J. Org. Chem. 2006, 71, 9522e9524; (h) Singh, B. K.; Appuk-
kuttan, P.; Claerhout, S.; Parmar, V. S.; der Eycken, E. V. Org. Lett. 2006, 8,
1863e1866; (i) Benard, S.; Neuville, L.; Zhu, J. J. Org. Chem. 2008, 73,
6441e6445; (j) Ley, S. V.; Thomas, A. W. Angew. Chem., Int. Ed. 2003, 42,
5400e5449; (k) Bolshan, Y.; Batey, R. A. Angew. Chem., Int. Ed. 2008, 47,
2109e2113; (l) He, C.; Chen, C.; Cheng, J.; Liu, C.; Liu, W.; Li, Q.; Lei, A. Angew.
Chem., Int. Ed. 2008, 47, 6414e6417; (m) Gonzallez, I.; Mosquera, J.; Guerrero,
C.; Rodriguez, R.; Cruces, J. Org. Lett. 2009, 11, 1677e1680.
13. (a) Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937e2940; (b)
Petrassi, H. M.; Sharpless, K. B.; Kelly, J. W. Org. Lett. 2001, 3, 139e142; (c)
Quach, T. D.; Batey, R. A. Org. Lett. 2003, 5, 1381e1384; (d) McKinley, N. F.;
OShea, D. F. J. Org. Chem. 2004, 69, 5087e5092; (e) Tzschucke, C. C.; Murphy, J.
M.; Hartwig, J. F. Org. Lett. 2007, 9, 761e764; (f) Shade, R. E.; Hyde, A. M.; Olsen,
J.-C.; Merlic, C. A. J. Am. Chem. Soc. 2010, 132, 1202e1203; (g) Wacharasindhu, S.;
Bardhan, S.; Wan, Z.-K.; Tabei, K.; Mansour, T. S. J. Am. Chem. Soc. 2009, 131,
4174e4175.
4.4.25. 2-Chlorophenyl 4-chlorophenyl sulfide (3y). Colorless oil.35
1H NMR (400 MHz, CDCl3):
d
¼7.40e7.37 (m, 1H), 7.33 (s, 4H),
7.15e7.10 (m, 2H), 7.01e6.98 (m, 1H). 13C NMR (100 MHz, CDCl3):
¼135.7, 134.4, 134.1, 133.8, 131.6, 130.6, 130.0, 129.8, 127.8, 127.4.
d
4.4.26. (4-Chlorophenylthio)naphthalene (3z). Colorless oil.15l 1H
NMR (400 MHz, CDCl3):
d
¼8.33e8.30 (m, 1H), 7.88e7.84 (m, 2H),
7.69e7.66 (m, 1H), 7.53e7.46 (m, 2H), 7.43 (t, J¼7.8 Hz, 1H), 7.15 (d,
J¼8.8 Hz, 2H), 7.06 (d, J¼8.8 Hz, 2H). 13C NMR (100 MHz, CDCl3):
d
¼135.8, 134.3, 133.6, 133.1, 132.0, 130.5, 129.9, 129.7, 129.2, 128.7,
127.2, 126.6, 125.9, 125.6.
4.4.27. 2-Chlorophenyl 2-methylphenyl sulfide (3a’). Colorless oil.
1H NMR (400 MHz, CDCl3):
d
¼7.42 (d, J¼7.6 Hz, 1H), 7.37e7.34 (m,
1H), 7.32e7.30 (m, 2H), 7.23e7.18 (m, 1H), 7.08e7.01 (m, 2H),
6.68e6.66 (m, 1H), 2.37 (s, 3H). 13C NMR (100 MHz, CDCl3):
d
¼142.0, 136.7, 135.4, 131.2, 131.0, 129.7, 129.5, 129.3, 128.3, 127.2,
127.1, 126.5, 20.6. Anal. Calcd for C13H11ClS: C, 66.51; H, 4.72; S,
13.66. Found: C, 66.23; H, 4.48; S, 13.51.
Acknowledgements
We thank the National Natural Science Foundation of China (No.
21272044) and Scientific Research Fund of Education Department
of Jiangxi Province (KJLD13022) for financial support.
Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2016.04.063.
References and notes
14. Herradura, P. S.; Pendola, K. A.; Guy, R. K. Org. Lett. 2000, 2, 2019e2022.
15. (a) Savarin, C.; Srogl, J.; Liebeskind, L. S. Org. Lett. 2002, 4, 4309e4312; (b)
Lengar, A.; Kappe, C. O. Org. Lett. 2004, 6, 771e774; (c) Beaulieu, C.; Guay, D.;
Wang, Z.; Evans, D. A. Tetrahedron Lett. 2004, 45, 3233e3236; (d) Huang, F.;
Batey, A. R. Tetrahedron 2007, 63, 7667e7672; (e) Taniguchi, N. Synlett 2006,
1351e1354; (f) Taniguchi, N. J. Org. Chem. 2007, 72, 1241e1245; (g) Pro-
kopcova, H.; Kappe, C. O. J. Org. Chem. 2007, 72, 4440e4448; (h) Kar, A.;
Sayyed, I. A.; Lo, W. F.; Kaiser, H. M.; Beller, M.; Tse, M. K. Org. Lett. 2007, 9,
3405e3408; (i) Kantam, M. L.; Neelima, B.; Sreedhar, B.; Chakravarti, R.
Synlett 2008, 1455e1458; (j) Luo, P.-S.; Wang, F.; Li, J.-H.; Tang, R.-Y.; Zhong, P.
Synthesis 2009, 921e928; (k) Jammi, S.; Sakthivel, S.; Rout, L.; Mukherjee, T.;
Mandal, S.; Mitra, R.; Saha, P.; Punniyamurthy, T. J. Org. Chem. 2009, 74,
1971e1976; (l) Xu, H.-J.; Zhao, Y.-Q.; Feng, T.; Feng, Y.-S. J. Org. Chem. 2012, 77,
2878e2884.
16. (a) Chiang, G. C. H.; Olsson, T. Org. Lett. 2004, 6, 3079e3082; (b) Girard, C.;
Onen, E.; Aufort, M.; Beauviere, S.; Samson, E.; Herscovici, J. Org. Lett. 2006, 8,
1689e1692; (c) Yang, J.; Li, P.; Wang, L. Tetrahedron 2011, 67, 5543e5549; (d)
Qzkai, E.; Ozcubukcu, S.; Jimeno, C.; Pericas, M. A. Catal. Sci. Technol. 2012, 2,
195e200.
17. (a) Benyahya, S.; Monnier, F.; Taillefer, M.; Wong Chi Man, M.; Bied, C.; Ouaz-
zani, F. Adv. Synth. Catal. 2008, 350, 2205e2208; (b) Benyahya, S.; Monnier, F.;
Wong Chi Man, M.; Bied, C.; Ouazzani, F.; Taillefer, M. Green Chem. 2009, 11,
1121e1123; (c) Coelho, A.; Diz, P.; Caamano, O.; Sotelo, E. Adv. Synth. Catal. 2010,
352, 1179e1192; (d) Miao, T.; Wang, L. Synthesis 2008, 363e368; (e) Zhang, L.;
Li, P.; Wang, L. Lett. Org. Chem. 2006, 3, 282e285.
18. (a) Chassaing, S.; Kumarraja, M.; Sido, A. S. S.; Pale, P.; Sommer, J. Org. Lett. 2007,
9, 883e886; (b) Chassaing, S.; Sido, A. S. S.; Alix, A.; Kumarraja, M.; Pale, P.;
Sommer, J. Chem.dEur. J. 2008, 14, 6713e6721.
19. Sharghi, H.; Khalifeh, R.; Doroodmand, M. M. Adv. Synth. Catal. 2009, 351,
207e218.
20. Lipshutz, B. H.; Taft, B. R. Angew. Chem., Int. Ed. 2006, 45, 8235e8238.
21. Sharghi, H.; Beyzavi, M. H.; Safavi, A.; Doroodmand, M. M.; Khalifeh, R. Adv.
Synth. Catal. 2009, 351, 2391e2410.
22. (a) Wang, D.; Etienne, L.; Echeverria, M.; Moya, S.; Astruc, D. Chem.dEur. J.
2014, 20, 4047e4054; (b) Yu, L.; Wang, M.; Li, P.; Wang, L. Appl. Organomet.
Chem. 2012, 26, 576e582; (c) Zeng, T.; Yang, L.; Hudson, R.; Song, G.; Moores, A.
R.; Li, C. J. Org. Lett. 2011, 13, 442e445; (d) Nasir Baig, R. B.; Varma, R. S. Green
Chem. 2012, 14, 625e632; (e) Nasir Baig, R. B.; Varma, R. S. Chem. Commun.
2012, 2582e2584.
1. (a) Nakazawa, T.; Xu, J.; Nishikawa, T.; Oda, T.; Fujita, A.; Ukai, K.; Mangindaan,
R. E. P.; Rotinsulu, H.; Kobayashi, H.; Namikoshi, M. J. Nat. Prod. 2007, 70,
439e442; (b) Liu, H.; Fujiwara, T.; Nishikawa, T.; Mishima, Y.; Nagai, H.; Shida,
T.; Tachibana, K.; Kobayashi, H.; Mangindaan, R. E. P.; Namikoshi, M. Tetrahedron
2005, 61, 8611e8615.
2. (a) Okamoto, T.; Mitsui, C.; Yamagishi, M.; Nakahara, K.; Soeda, J.; Hirose, Y.;
Miwa, K.; Sato, H.; Yamano, A.; Matsushita, T.; Uemura, T.; Takeya, J. Adv. Mater.
2013, 25, 6392e6397; (b) Mori, T.; Nishimura, T.; Yamamoto, T.; Doi, I.; Miya-
zaki, E.; Osaka, I.; Takimiya, K. J. Am. Chem. Soc. 2013, 135, 13900e13913; (c)
Takimiya, K.; Shinamura, S.; Osaka, I.; Miyazaki, E. Adv. Mater. 2011, 23,
4347e4370.
3. (a) Krapcho, J.; Spitzmiller, E. R.; Turk, C. F. J. Med. Chem. 1963, 6, 544e546; (b)
Krapcho, J.; Turk, C. F. J. Med. Chem. 1966, 9, 191e195; (c) Nielsen, S. F.; Nielsen,
E. O.; Olsen, G. M.; Liljefors, T.; Peters, D. J. Med. Chem. 2000, 43, 2217e2226; (d)
De Martino, G.; La Regina, G.; Coluccia, A.; Edler, M. C.; Barbera, M. C.; Brancale,
A.; Wilcox, E.; Hamel, E.; Artico, M.; Silvestri, R. J. Med. Chem. 2004, 47,
6120e6123; (e) Pasquini, S.; Mugnaini, C.; Tintori, C.; Botta, M.; Trejos, A.; Ar-
vela, R. K.; Larhed, M.; Witvrouw, M.; Michiels, M.; Christ, F.; Debyser, Z.;
Corelli, F. J. Med. Chem. 2008, 51, 5125e5129.
4. (a) Thuillier, A.; Metzner, P. Sulfur Reagents in Organic Synthesis; Academic
Press: New York, 1994; (b) Ruano, J. L. G.; Aleman, J.; Fajardo, C.; Parra, A. Org.
Lett. 2005, 7, 5493e5496; (c) Kamata, K.; Hirano, T.; Mizuno, N. Chem. Commun.
2009, 3958e3960; (d) Rostami, A.; Akradi, J. Tetrahedron Lett. 2010, 51,
3501e3503; (e) Bahrami, K.; Khodaei, M. M.; Sohrabnezhad, S. Tetrahedron Lett.
2011, 52, 6420e6423; (f) Boruah, J. J.; Das, S. P.; Ankireddy, S. R.; Gogoi, S. R.;
Islam, N. S. Green Chem. 2013, 15, 2944e2959.
5. (a) Mellah, M.; Voituriez, A.; Schulz, E. Chem. Rev. 2007, 107, 5133e5209; (b) Li,
Y.; Xu, M. H. Chem. Commun. 2014, 3771e3782.
6. (a) Metal-catalyzed Cross-coupling Reactions; de Meijere, A., Diederich, F., Eds.;
Wiley-VCH: Weinheim, 2004; (b) Catalyzed Carbon-heteroatom Bond Formation;
Yudin, A. K., Ed.; Wiley-VCH: Weinheim, 2011; (c) Surry, D. S.; Buchwald, S. L.
Chem. Sci. 2011, 2, 27e50.
7. For reviews and selected examples, see (a) Beletskaya, I. P.; Ananikov, V. P.
Chem. Rev. 2011, 111, 1596e1636; (b) Hartwig, J. F. Acc. Chem. Res. 2008, 41,
1534e1544; (c) Murata, M.; Buchwald, S. L. Tetrahedron 2004, 60, 7397e7403;
(d) Kosugi, M.; Ogata, T.; Terada, M.; Sano, H.; Migita, T. Bull. Chem. Soc. Jpn.
1985, 58, 3657e3658; (e) Itoh, T.; Mase, T. Org. Lett. 2004, 6, 4587e4590; (f)
Fernandez-Rodriguez, M. A.; Shen, Q.-L.; Hartwig, J. F. J. Am. Chem. Soc. 2006,
128, 2180e2181; (g) Eichman, C. C.; Stambuli, J. P. J. Org. Chem. 2009, 74,
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063

Y. Lin et al. / Tetrahedron xxx (2016) 1e9
9
23. (a) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature
1992, 359, 710e714; (b) Jia, M.; Seifert, A.; Thiel, W. R. Chem. Mater. 2003, 15,
2174e2180; (c) Taguchi, A.; Schuth, F. Microporous Mesoporous Mater. 2005, 77,
1e45; (d) Martin-Aranda, R. M.; Cejka, J. Top. Catal. 2010, 53, 141e153.
24. Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K. D.;
Chu, C. T.-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.; Higgins, J. B.;
Schlenker, J. L. J. Am. Chem. Soc. 1992, 114, 10834e10843.
R.; Yao, R.; Cai, M. Eur. J. Org. Chem. 2012, 4178e4184; (i) Zhao, H.; He, W.; Yao,
R.; Cai, M. Adv. Synth. Catal. 2014, 356, 3092e3098.
26. Lim, M. H.; Stein, A. Chem. Mater. 1999, 11, 3285e3295.
27. Li, M.-J.; Chen, Z.; Wing-Wah Yam, V.; Zu, Y. ACSNANO 2008, 2, 905e912.
28. Reddy, V. P.; Kumar, A. V.; Swapna, K.; Rao, K. R. Org. Lett. 2009, 11, 1697e1700.
29. Petrillo, M.; Novi, G.; Garbarino, G.; Dell’Erba, T. Tetrahedron 1986, 42,
4007e4016.
25. (a) Mehnert, P. C.; Weaver, D. W.; Ying, J. Y. J. Am. Chem. Soc. 1998, 120,
12289e12296; (b) Shyu, S.-G.; Cheng, S.-W.; Tzou, D.-L. Chem. Commun. 1999,
2337e2338; (c) Mukhopadhyay, K.; Sarkar, B. R.; Chaudhari, R. V. J. Am. Chem.
Soc. 2002, 124, 9692e9693; (d) Nunes, C. D.; Valente, A. A.; Pillinger, M.; Fer-
nandes, A. C.; Romao, C. C.; Rocha, J.; Goncalves, I. S. J. Mater. Chem. 2002, 12,
1735e1742; (e) Baleizao, C.; Corma, A.; Garcia, H.; Leyva, A. J. Org. Chem. 2004,
69, 439e446; (f) Cai, M.; Zheng, G.; Ding, G. Green Chem. 2009, 11, 1687e1693;
(g) Cai, M.; Peng, J.; Hao, W.; Ding, G. Green Chem. 2011, 13, 190e196; (h) Xiao,
30. Wang, L.; Chen, Z.-C. Synth. Commun. 2001, 31, 1227e1232.
31. Yanez, C. O.; Andradea, C. D.; Belfield, K. D. Chem. Commun. 2009, 827e829.
32. Reddy, V. P.; Swapna, K.; Kumar, A. V.; Rao, K. R. J. Org. Chem. 2009, 74,
3189e3191.
33. Norris, T.; Leeman, K. Org. Process Res. Dev. 2008, 12, 869e876.
34. Fujisawa, T. Tetrahedron Lett. 1968, 5071e5074.
35. Zhang, X. Chin. J. Org. Chem. 2011, 31, 1107e1113.
Please cite this article in press as: Lin, Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.04.063