Nickel-Catalyzed C–S Coupling: Synthesis of Diaryl Sulfides Starting from Phenyldithiocarbamates and Iodobenzenes

Article abstract of DOI:10.1002/ejoc.201701081

A nickel-catalyzed C–S bond-formation protocol for the synthesis of diaryl sulfides is described. In a reaction catalyzed by NiCl₂, phenyldithiocarbamates react with iodobenzenes to give diaryl sulfides smoothly in good to excellent yields (66–93 %). The catalyst is cheap, the reaction is easy to carry out, the substrate scope is broad, and the yields are good. Thus, this gives an alternative way to prepare diaryl sulfides.

Full text of DOI:10.1002/ejoc.201701081

A Journal of
Accepted Article
Title: Nickel-catalyzed C-S coupling: synthesis of diarylsulfides starting
from phenyldithiocarbamates and iodobenzenes
Authors: Zhi-Bing Dong, Xing Liu, Qiang Cao, Wan Xu, and Meng-Tian
Zeng
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701081
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701081
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10.1002/ejoc.201701081
European Journal of Organic Chemistry
FULL PAPER
Nickel-catalyzed C-S coupling: synthesis of diarylsulfides starting
from phenyldithiocarbamates and iodobenzenes
Xing Liu,+ Qiang Cao,+ Wan Xu, Meng-Tian Zeng, Zhi-Bing Dong*
Dedicated to Prof. Herbert Mayr at Ludwig-Maximilians Universität on the occasion of his 70th birthday
Abstract:
A
Nickel catalyzed C-S formation protocol for the
unsatisfying yields, high catalyst/ligand loading, using big excess
of the sulfur reagents.
synthesis of diarylsulfides was developed. Catalyzed by NiCl2,
phenyldithiocarbamates reacted with iodobenzenes furnishing
diarylsulfides smoothly with good to excellent yields (66-93%). The
protocol has the features of cheap catalyst, easy performance, broad
substrate scope and nice yields, affording an alternative way for the
preparation of diarylsulfides.
Dithiocarbamates constitute an important class of compounds
that are known to have a wide range of biological activities.
Moreover, they could be used as versatile synthetic
intermediates in organic synthesis.[16] As a part of our continued
efforts[17] to explore modified protocols for the C-S formation
reactions, we describe herein an efficient method for the
synthesis of diarylsulfides via the cross-coupling of
phenlyldithiocarbamates with aryl iodides using NiCl2 as catalyst,
affording an alternative way for the preparation of diarylsulfides.
Introduction
Diarylsulfides are valuable intermediates in the construction of
biologically and pharmaceutically active molecules and organic
materials,[1] some medical agents containing diaryl sulfide
structure are employed in various clinical applications such as
cancer, inflammation, alzheimer, parkinson and HIV infections.[2]
Therefore, exploration of efficient and facile protocols for the
Caryl-S bond formation under environmentally benign conditions
is highly desirable. Transition-metal-catalyzed Caryl-S cross-
coupling reaction (Pd,[3] Ni,[4] Fe,[5] Co,[6] In,[7] and Cu.[8]) is a
powerful protocol for the construction of this important block and
the related approaches mainly focus on the cross-coupling of
aryl halides with thiols.[9] Though efficient, the reported methods
have some drawbacks, such as using smelling and hazardous
thiols which could act as metal deactivators due to their
tendency to bind to transition metals. Thus, the deactivation of
transition metal catalysts forced chemists to use high catalyst
loadings, specially designed ligands, high temperature, strong
base, leading to high costs and the incompatibility of some
functional groups. To overcome the above problems, the
development of new sustainable and effective sulfur transferring
reagents is a hot topic. So far, recent advances in this field have
described the use of thioacetamide,[10] dithiooxamide,[11]
Results and Discussion
We undertook an investigation of the reactivity of
phenyldithiocarbamate (1a) in nickel-catalyzed cross-coupling
reaction with 1-iodo-4-methyl-benzene (2a).
A series of
experiments were performed by varying reaction parameters,
such as catalysts, additions, ligands, solvents and temperature
(Table 1). At first, we employed a number of Nickel salts (5
mol%) and N,N-ligands to catalyze the model reaction (Table 1,
Entries 1-11). Gratifyingly, the desired product (3a, 1-methyl-4-
phenylsulfanyl-benzene) could be obtained in 71 % isolation
yield by using NiCl2 as catalyst, 2,2'-bipyridine as ligand, zinc
powder as additive (Table 1, Entry 2). Other nickel catalysts
.
(NiBr2, NiCl2 6H2O in Table 1, Entries 3-4) showed a less
reactivity. The solvent survey (Table 1, Entries 2, 5-6) showed
that DMF was the most suitable solvent. Control experiments for
the ligands examination listed in entries 7-11 showed that 2,2'-
bipyridine as ligand was crucial for the reaction, and the ligand
loading should be set as 10 mol%. The temperature examination
(Table 1, Entries 6, 12-13) showed that 110oC was the optimal
reaction temperature. In addition, the loading ratio of NiCl2 was
investigated (Table 1, Entries 6, 14-15), and it revealed that 5
mol% of Nickel salt was the best. Furthermore, the studies on
loading of Zinc powder and other metal additives (Mg, Fe)
showed that Zinc was the most efficient and the loading should
be set as 200 mol% (Table 1, Entries 16-19). The optimized
reaction conditions were summarized in Entry 6, Table 1.
thiourea,[12]
disulfides,[13]
2-thiobenzamides[14]
and
N-
thioimides[15] as thiols surrogate to form biarylsulfides. While
these methods still suffer from disadvantages, including
[*]
[+]
School of Chemistry and Environmental Engineering, Wuhan
Institute of Technology, Wuhan 430205, China
E-mail: dzb04982@wit.edu.cn
These authors contributed equally to this work.
Table 1. Optimization of the reaction conditions.[a]
I
S
N
Conditions
+
S
S
3a
1a
2a
Entry
Catalysts
Additives
Ligands
Solvents
T(oC)
Yields[b]
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10.1002/ejoc.201701081
European Journal of Organic Chemistry
FULL PAPER
OH
(mol%)
NiCl2 (5%)
NiCl2 (5%)
NiBr2 (5%)
NiCl2·6H2O
(5%)
(equiv)
--
HO
S
N
N
I
1
2
3
bpy
bpy
bpy
DMSO
DMSO
DMSO
DMSO
110
110
110
110
N.R
71%
65%
Zn (2.0)
Zn (2.0)
6
7
S
S
3f : 80%
1a
2f
I
4
Zn (2.0)
bpy
45%
S
5
6
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
Zn(2.0)
Zn (2.0)
Zn (2.0)
Zn (2.0)
Zn (2.0)
Zn (2.0)
Zn (2.0)
bpy
bpy
DMAc
DMF
DMF
DMF
DMF
DMF
DMF
110
110
110
110
110
110
110
80%
86%
trace
66%
trace
trace
S
S
S
3g : 86%
1a
2g
2h
2i
7
8[c]
--
I
bpy
S
N
N
N
9
DMEDA
L-proline
8
9
10
S
1a
3h : 85%
1,10-
phenanth
roline
I
Cl
11
63%
S
12
13
14
15
16
17
18
19
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (10%)
NiCl2 (1%)
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
NiCl2 (5%)
Zn (2.0)
Zn (2.0)
Zn (2.0)
Zn (2.0)
Zn (1.5)
Zn (1.0)
Mg (2.0)
Fe (2.0)
bpy
bpy
bpy
bpy
bpy
bpy
bpy
bpy
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
130
90
87%
75%
87%
45%
73%
55%
37%
trace
S
S
S
Cl
3i : 86%
1a
110
110
110
110
110
110
I
Br
S
10
S
Br
3j : 88%
2j
1a
S
N
I
[a]Reaction conditions: 1a (1.0 mmol), 2a (1.2 mmol), [Ni]: x mol%, ligand (10
mol%), additive, solvent (2 mL) in a sealed tube, heat for 18 h. [b]Isolated
yields. [c]Bipyridine: 5 mol%.
11
12
13
S
S
1b
3k : 66%
2a
OH
HO
S
N
I
To study the generality of the substrate scope, a range of
phenyldithiocarbamates and iodobenzenes were submitted for
survey under the optimized reaction conditions (Table 2). To our
delight, all the selected phenyldithiocarbamates and
iodobenzenes reacted well, giving the symmetric or unsymmetric
biarylsulfides (3a-3q) smoothly with good to excellent yields. It
S
S
3l : 69%
1b
2f
Cl
I
S
N
S
S
Cl
1c
2a
3m : 90%
was
found
that
the
electronic
nature
of
the
phenyldithiocarbamates and iodobenzenes played either little or
no effect on the reaction, which revealed the versatility of this
protocol.
S
N
I
S
14
15
16
17
S
2a
2a
3n : 85%
1d
Table
2.
Ni-catalyzed
synthesis
of
biarylsulfides
starting
phenyldithiocarbamates and iodobenzenes. [a]
S
N
I
NiCl2 ( 5 mol% )
bpy ( 10 mol% )
S
N
I
R1
R2
S
R1
R2
+
S
S
Zn, DMF, 110oC
S
1e
3o : 81%
1
2
3
I
S
N
F3C
Product 3
Entry
1
Substrate 1
Substrate 2
Yields[b]
S
F3C
S
S
N
1f
I
3p : 82%
2a
2a
S
S
S
S
N
I
3a : 86%
1a
2a
S
S
N
I
F C
3
S
CF
3
3q : 81%
2
3
S
1g
[a]Reaction conditions: 1 (1.0 mmol), 2 (1.2 mmol), NiCl2 (5% mol), bipyridine
(10% mol), Zn (200% mmol), DMF (2 mL) in a sealed tube at 110 oC for 18 h.
[b]Isolated yields.
1a
2b
3b : 79%
S
N
I
S
S
S
S
According to the experimental results and reported
literature,[18] a plausible reaction mechanism is proposed in
Scheme 1. First, NiCl2 was reduced to Ni0 and stabilized with
ligand (Ln=bipyridine, n=2). Ni0 went through oxidative addition
with aryl iodide to give intermediate Ar1NiIIILn (A). By reacting
with phenyldithiocarbamate, the transition state (B) might be
formed transiently. The subsequent metathesis type reaction
gave thiocarbamoyl iodide (C) and the transmetallated
2c
1a
3c : 83%
I
S
N
N
4
5
S
1a
3d : 69%
2d
I
OH
S
S
HO
3e : 93%
2e
1
2
1a
Ⅱ
intermediate LnAr Ni SAr (D). At last, the reductive elimination
of (D) furnished the desired cross-coupling product Ar1SAr2 (E)
while regenerating the Ni0 catalyst.
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10.1002/ejoc.201701081
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Ln = Bpy
anhydrous Na2SO4 and evaporated under vacuum. The residue was
purified by flash column chromatography to afford the desired product.
Ar1SAr2
LnNi0
(E)
Ar1I
1-Methyl-4-phenylsulfanyl-benzene (3a). According to TP, the residue
was purified by flash chromatography on silica gel to (eluent: petroleum
ether) give the target compound 3a (yield = 86%) as a colorless oil. 1H
NMR (400 MHz, CDCl3) δ: 7.04-6.85 (m, 9H), 2.06 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 137.6, 137.1, 132.3, 131.3, 130.1, 129.8, 129.1, 126.4,
21.1; HRMS (ESI): calcd for C13H12S (200.0660), found: 200.0672.
Zn
NiCl2
Ar1Ni LnI
Ⅱ
LnAr1Ni SAr2
Ⅱ
(A)
(D)
Diphenyl sulfide (3b). According to TP, the residue was purified by flash
chromatography on silica gel to (eluent: petroleum ether) give the target
compound 3b (yield = 79%) as a colorless oil. 1H NMR (400 MHz, CDCl3)
δ: 7.43-7.29 (m, 10H); 13C NMR (100 MHz, CDCl3) δ: 135.8, 131.1,
S
N(CH3)2
Ar2SCN(CH3)2
S
I
C
S
ICN(CH3)2
129.2, 127.1; HRMS (ESI): calcd for C13H12S (186.0503), found:
(C)
186.0522.
LnAr1Ni
SAr2
Ⅱ
(B)
1-Methyl-3-phenylsulfanyl-benzene (3c). According to TP, the residue
was purified by flash chromatography on silica gel to (eluent: petroleum
ether) give the target compound 3c (yield = 83%) as a colorless oil. 1H
NMR (400 MHz, CDCl3) δ: 7.42-7.11 (m, 9H), 2.36 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 139.0, 136.2, 135.3, 131.9, 130.8, 129.2, 129.1, 128.4,
128.1, 126.9, 21.3; HRMS (ESI): calcd for C13H12S 200.0660, found:
200.0671.
Scheme 1. Plausible mechanism of the reaction.
Conclusions
In summary, we presented an alternative method for the
preparation
phenyldithiocarbamates.
of
biarylsulfides
Catalyzed
starting
by
from
NiCl2,
1-Methyl-2-phenylsulfanyl-benzene (3d). According to TP, the residue
was purified by flash chromatography on silica gel to (eluent: petroleum
ether) give the target compound 3d (yield = 69%) as a colorless oil. 1H
NMR (400 MHz, CDCl3) δ: 7.27-7.07 (m, 9H), 2.34 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 139.9, 136.2, 133.7, 133.0, 130.6, 129.6, 129.1, 127.9,
126.7, 126.3, 20.6; HRMS (ESI): calcd for C13H12S (200.0660), found:
200.0674.
phenyldithiocarbamates reacted with iodobenzenes furnishing
diarylsulfides smoothly with good to excellent yields (66-93%).
Cheap catalyst, easy performance, broad substrate scope and
nice yields are important features of this new method, affording
an alternative way for the construction of C-S bond. Further
investigation of this protocol and the related applications are
currently under research in our laboratory.
4-Phenylsulfanyl-phenol (3e). According to TP, the residue was purified
by flash chromatography on silica gel to (eluent: petroleum ether/ethyl
acetate=5:1) give the target compound 3e (yield = 93%) as a yellow oil.
1H NMR (400MHz, CDCl3) δ: 7.32 (d, J = 8.0 Hz, 2H), 7.23-7.10 (m, 5H),
6.79 (d, J = 8.0 Hz, 2H), 5.09 (brs, 1H); 13C NMR (100 MHz, CDCl3) δ:
155.8, 138.2, 135.5, 129.0, 128.3, 125.9, 124.5, 116.6; HRMS (ESI):
calcd for C12H10OS (202.0452), found: 202.0461.
Experimental Section
All starting materials were purchased from commercial suppliers and
used without further purification unless otherwise stated. Yields refer to
isolated compounds estimated to be 95% pure as determined by 1H
NMR and capillary GC analysis. NMR spectra were recorded on a Bruker
AM400 NMR instrument in CDCl3 using TMS as an internal standard.
Chemical shifts are given in ppm and coupling constants (J) are given in
Hz. All melting points were determined on a RY-1G melting point
instrument without correction. High-resolution mass spectra (HRMS)
were recorded on a Finnigan MAT 95Q or Finnigan 90 mass instrument
(ESI). TLC was performed using aluminum plates coated with SiO2
(Merck 60, F-254) and visualized with UV light at 254 nm. Column
chromatography was performed on silica gel with PE-EtOAc as the
eluent.
2-Phenylsulfanyl-phenol (3f). According to TP, the residue was purified
by flash chromatography on silica gel to (eluent: petroleum ether/ethyl
acetate=20:1) give the target compound 3f (yield = 80%) as a colorless
oil. 1H NMR (400MHz, CDCl3) δ: 7.49-6,87 (m, 9H), 6.52 (brs, 1H); 13C
NMR (100 MHz, CDCl3) δ: 157.3, 136.9, 135.9, 132.3, 129.2, 126.9,
126.1, 121.3, 116.3, 115.6; HRMS (ESI): calcd for C12H10OS (202.0452),
found: 202.0466.
1-nButyl-4-phenylsulfanyl-benzene (3g). According to TP, the residue
was purified by flash chromatography on silica gel to (eluent: petroleum
ether) give the target compound 3g (yield = 86%) as a colorless oil. 1H
NMR (400MHz, CDCl3) δ: 7.29-7.08 (m, 9H), 2.56 (t, J = 8.0 Hz, 2H),
1.56 (t, J = 8.0 Hz, 2H), 1.34 (t, J = 8.0 Hz, 2H), 0.91 (t, J = 8.0 Hz, 3H);
13C NMR(100 MHz, CDCl3): δ: 142.5, 137.1, 132.1, 131.6, 129.9, 129.4,
Typical procedure for the preparation of diaryl sulfide (TP)
Dimethyl-dithiocarbamic acid phenyl ester (1a, 1.0 mmol), 1-iodo-4-
methyl-benzene (2a, 1.2 mmol), NiCl2 (5 mol%), bpy (10 mol%) and Zn
(200 mmol%) were added in dried seal tube equipped with a septum and
magnetic stirring bar, DMF (2 mL) was then added. The mixture was
stirred at 110 oC and checked by TLC until the starting material was
finished (about 18 h). The reaction was cooled down to room
temperature, quenched with sat. NH4Cl solution (5 mL) and then
extracted with ethyl acetate. The crude solution was dried over
129.1, 126.5, 35.3, 33.5, 22.4, 14.0; HRMS (ESI): calcd for C16H18
(242.1129), found: 242.1129.
S
1,3-Dimethyl-5-phenylsulfanyl-benzene (3h). According to TP, the
residue was purified by flash chromatography on silica gel to (eluent:
petroleum ether) give the target compound 3h (yield = 85%) as a
colorless oil. 1H NMR 400 MHz, CDCl3) δ: 7.30-7.16 (m, 5H), 6.98 (s, 2H),
6.84 (s, 1H), 2.22 (s, 6H); 13C NMR (100 MHz, CDCl3) δ: 138.9, 136.5,
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10.1002/ejoc.201701081
European Journal of Organic Chemistry
FULL PAPER
134.8, 130.5, 129.2, 129.2, 129.1, 126.7, 21.2; HRMS (ESI): calcd for
C14H14S (214.0816), found: 214.0831.
petroleum ether) give the target compound 3p (yield = 82%) as a white
solid. Mp: 91-93 oC. 1H NMR (400 MHz, CDCl3) δ: 7.48-7.41 (m, 4H),
7.24-7.21 (m, 4H), 2.40 (s, 3H); 13C NMR (100 MHz) δ: 143.9, 139.3,
134.3, 130.6, 128.3, 127.6 (q, J = 33 Hz), 127.4, 125.7 (q, J = 4 Hz),
124.2 (q, J = 270 Hz), 21.3; HRMS (ESI): calcd for C14H11F3S (268.0534),
found: 268.0541.
1-Chloro-4-phenylsulfanyl-benzene (3i). According to TP, the residue
was purified by flash chromatography on silica gel to (eluent: petroleum
ether) give the target compound 3i (yield = 86%) as a colorless oil. 1H
NMR 400 MHz, CDCl3) δ: 7.42-7.30 (m, 9H); 13C NMR (100 MHz, CDCl3)
δ: 135.2, 134.7, 133.0, 132.1, 131.4, 129.4, 129.4, 127.5; HRMS (ESI):
calcd for C12H9ClS (220.0113), found: 222.0121.
3-Trifluoromethylphenyl-4-methylphenyl sulfide (3q). According to TP,
the residue was purified by flash chromatography on silica gel to (eluent:
petroleum ether) give the target compound 3q (yield = 81%) as a
colorless oil. 1H NMR (400 MHz, CDCl3) δ: 7.36 (s, 1H), 7.28-7.21 (m,
5H), 7.08 (d, J = 8.0 Hz, 2H), 2.26 (s, 3H); 13C NMR (100 MHz) δ: 139.8,
138.9, 133.5, 131.6, 131.4 (q, J = 32 Hz), 130.5, 129.4, 129.2, 125.4 (q, J
= 270 Hz), 125.1 (q, J = 3 Hz), 122.6 (q, J = 3 Hz), 21.2; HRMS (ESI):
calcd for C14H11F3S (268.0534), found: 268.0543.
1-Bromo-4-phenylsulfanyl-benzene (3j). According to TP, the residue
was purified by flash chromatography on silica gel to (eluent: petroleum
ether) give the target compound 3j (yield = 88%) as a yellow oil. 1H NMR
400 MHz, CDCl3) δ: 7.30-7.16 (m, 7H), 7.06 (d, J = 8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ: 135.5, 134.8, 132.2, 132.2, 131.6, 129.4, 127.6,
120.9; HRMS (ESI): calcd for C12H9BrS (263.9608), found: 263.9621.
Bis(p-Tolyl) sulfide (3k). According to TP, the residue was purified by
flash chromatography on silica gel to (eluent: petroleum ether) give the
target compound 3k (yield = 66%) as a white solid. Mp: 56-58 oC. 1H
NMR (400 MHz, CDCl3) δ: 7.21 (d, J = 8.0 Hz, 4H), 7.07 (d, J = 8.0 Hz,
4H), 2.29 (s, 6H); 13C NMR (100 MHz, CDCl3) δ: 136.8, 132.6, 131.0,
129.9, 21.0; HRMS (ESI): calcd for C14H14S (214.0816), found: 214.0828.
Acknowledgements
We thank the foundation support from National Natural Science
Foundation of China (21302150) Hubei Provincial Department of
Education (D20131501), Scientific Research Foundation for the
Returned Overseas Chinese Scholars, State Education Ministry
[2012]1707, foundation of Chutian distinguished fellow from
Hubei Provincial Department of Education. We thank Prof.
Aiwen Lei at Wuhan Univesity (China) for generous NMR
analysis support, we also thank Prof. Paul Knochel at Ludwig-
Maximilians Universität (Germany) for helpful discussions.
2-(p-tolylthio)phenol (3l). According to TP, the residue was purified by
flash chromatography on silica gel to (eluent: petroleum ether/ethyl
acetate=7:1) give the target compound 3l (yield = 69%) as a colorless oil.
1H NMR (400 MHz, CDCl3) δ: 7.52-7.50 (m, 1H), 7.36-7.32 (m, 1H), 7.06-
7.00 (m, 5H), 6.94-6.90 (m, 1H), 6.55 (brs, 1H), 2.27 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 157.0, 136.6, 136.2, 132.1, 131.9, 129.9, 127.4,
121.1, 117.1, 115.4, 20.9; HRMS (ESI): calcd for C13H12OS (216.0609),
found: 216.0621.
Keywords: Nickel • phenyldithiocarbamate • iodobenzene •
diarylsulfide • catalysis
2-Chlorophenyl-4-methylphenyl sulfide (3m). According to TP, the
residue was purified by flash chromatography on silica gel to (eluent:
petroleum ether) give the target compound 3m (yield = 90%) as a
colorless oil. 1H NMR (400 MHz, CDCl3) δ: 7.34-7.29 (m, 3H), 7.16 (d, J
= 8.0 Hz, 2H), 7.03-7.00 (m, 2H), 6.83-6.81 (m, 1H), 2.34 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 138.9, 137.6, 134.2, 132.0, 130.4, 129.5,
128.8, 128.3, 127.0, 126.5, 21.2; HRMS (ESI): calcd for C13H11ClS
(234.0270), found: 234.0283.
[1]
a) M. L. Alcaraz, S. Atkinson, P. Cornwall, A. C. Foster, D. M. Gill, L. A.
Humphries, P. S. Keegan, R. Kemp, E. Merifield, R. A. Nixon, Org.
Process. Res. Dev. 2005, 9, 555-569; b) B. Bonnet, D. Soullez, S.
Girault, L. Maes, V. Landry, E. Davioud-Charvet, C. Sergheraert,
Bioorgan. Med. Chem. 2000, 8, 95-103; c) G. Liu, J. Link, Z. Pei, E. B.
Reilly, S. Leitza, B. Nguyen, K. C. Marsh, G. F. Okasinski, T. W. von
Geldern, M. Ormes, J. Med. Chem. 2000, 43, 4025-4040; d) B. R.
Vaddula, R. S. Varma, J. Leazer, Eur. J. Org. Chem. 2012, 2012, 6852-
6855.
4-nButylphelyl-4-methylphenyl sulfide (3n). According to TP, the
residue was purified by flash chromatography on silica gel to (eluent:
petroleum ether) give the target compound 3n (yield = 85%) as a
colorless oil. 1H NMR (400 MHz, CDCl3) δ: 7.24-7.19 (m, 4H), 7.08 (d, J
= 8.0 Hz, 4H), 2.56 (t, J = 8.0 Hz, 2H), 2.30 (s, 3H), 1.56 (t, J = 8.0 Hz,
2H), 1.33 (d, J = 8.0 Hz, 2H), 0.91(t, J = 8.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ: 141.8, 136.9, 132.9, 132.5, 131.2, 130.8, 129.9, 129.2, 35.2,
33.5, 22.3, 21.0, 13.9; HRMS (ESI): calcd for C17H20S (256.1286), found:
256.1291.
[2]
a) G. De Martino, M. C. Edler, G. La Regina, A. Coluccia, M. C.
Barbera, D. Barrow, R. I. Nicholson, G. Chiosis, A. Brancale, E. Hamel,
J. Med. Chem. 2006, 49, 947-954; b) S. W. Kaldor, V. J. Kalish, J. F.
Davies, B. V. Shetty, J. E. Fritz, K. Appelt, J. A. Burgess, K. M.
Campanale, N. Y. Chirgadze, D. K. Clawson, J. Med. Chem. 1997, 40,
3979-3985; c) H. N. Tinsley, B. D. Gary, A. B. Keeton, W. Lu, Y. Li, G.
A. Piazza, Cancer. Prev. Res. 2011, 4, 1275-1284; d) H. Tsutsui, Y.
Hayashi, K. Narasaka, Chem. Lett. 1997, 26, 317-318.
[3] T. Itoh, T. Mase, Org. Lett. 2004, 6, 4587-4590.
[4] a) A. R. Hajipour, M. Karimzadeh, G. Azizi, Chinese Chem. Lett. 2014,
25, 1382-1386; b) M. Soleiman-Beigi, Z. Arzehgar, Heteroatom. Chem.
2015, 26, 355-360; c) M. Soleiman-Beigi, F. Mohammadi, Synlett. 2015,
26, 911-914; d) Y. Zhang, K. C. Ngeow, J. Y. Ying, Org. Lett. 2007, 9,
3495.
3,5-Dimethylphenyl-4-methylphenyl sulfide (3o). According to TP, the
residue was purified by flash chromatography on silica gel to (eluent:
petroleum ether) give the target compound 3o (yield = 81%) as a
colorless oil. 1H NMR (400 MHz, CDCl3) δ: 7.26 (d, J = 8.0 Hz, 2H), 7.09
(d, J = 8.0 Hz, 2H), 6.91 (s, 2H), 6.82 (s, 1H), 2.31 (s, 3H), 2.23 (s, 6H);
13C NMR (100 MHz, CDCl3) δ: 138.7, 137.1, 136.1, 131.8, 131.7, 129.9,
128.5, 127.9, 21.2, 21.1; HRMS (EI): calcd for C15H16S (228.0973),
found: 228.0981.
[5] W. Y. Wu, J. C. Wang, F. Y. Tsai, Green Chem. 2009, 11, 326-329.
[6] Y. C. Wong, T. T. Jayanth, C. H. Cheng, Org. Lett. 2006, 8, 5613-5616.
[7] V. P. Reddy, K. Swapna, A. V. Kumar, K. R. Rao, Cheminform. 2009,
40, 3189-3191.
4-Trifluoromethylphenyl-4-methylphenyl sulfide (3p). According to TP,
the residue was purified by flash chromatography on silica gel to (eluent:
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[8] a) M. S. Kabir, M. Lorenz, M. L. Van Linn, O. A. Namjoshi, S. Ara, J. M.
Cook, J. Org. Chem. 2010, 41, 3626-3643; b) F. Luo, C. Pan, L. Li, F.
Chen, J. Cheng, Chem. Commun. 2011, 42, 5304-5306.
[14] (a) A. Henke, J. Srogl, Chem. Commun. 2011, 47, 4282-4284; (b) J. M.
Villalobos, J. Srogl, L. S. Liebeskind, J. Am. Chem. Soc. 2007, 129,
15734-15735.
[9]
a) C. G. Bates, R. K. Gujadhur, D. Venkataraman, Org. Lett. 2003, 44,
81-84; b) M. Carril, R. SanMartin, E. Domínguez, I. Tellitu, Chem. Eur.
J. 2007, 13, 5100-5105; c) M. A. Fernandez Rodriguez, Q. Shen, J. F.
Hartwig, J. Am. Chem. Soc. 2006, 128, 2180-2181; d) Z. Jiang, J. She,
X. Lin, Adv. Synth. Catal. 2009, 351, 2558-2562; e) A. Kamal, V.
Srinivasulu, J. N. S. R. C. Murthy, N. Shankaraiah, N. Nagesh, T. S.
Reddy, A. V. S. Rao, Adv. Synth. Catal. 2013, 355, 2297-2307; f) J.
She, Z. Jiang, Y. Wang, Tetrahedron Lett. 2009, 50, 593-596.
[15] (a) R. Pluta, P. Nikolaienko, M. Rueping, Angewandte. Chemie. 2014,
126, 1676-1679; (b) C. Savarin, J. Srogl, L.S. Liebeskind, Org. Lett.
2002, 4, 4309-4312.
[16] a) A. K. Mukerjee, R. Ashare, Chem. Rev. 1991, 91, 1-24; b) U. Boas,
H. Gertz, J. B. Christensen, P. M. Heegaard, Tetrahedron Lett. 2004,
45, 269-272.
[17] a) Q. Cao, F. Liu, M. Wang, W. Xu, M. T. Zeng, M. Liu, Y. S. Li, Z. B.
Dong, J. Chem. Res., 2017, 41, 301-303; b) M. T. Zeng, W. Xu, M. Liu,
X. Liu, C. Z. Chang, H. Zhu, Z. B. Dong, Synopen. 2017, 1, 1-7; c) W.
Xu, M. T. Zeng, M. Liu, S. S. Liu, Y. S. Li, Z. B. Dong, Synthesis 2017,
49, 3084-3090.
[10] a) N. Taniguchi, Synlett. 2005, 36, 1687-1690; b) N. Taniguchi,
Tetrahedron. 2012, 68, 10510-10515.
[11] H. Firouzabadi, N. Iranpoor, F. Gorginpour, A. Samadi, Eur. J. Org.
Chem. 2015, 2015, 2914-2920.
[18] a) M. Abbasi, N. Nowrouzi, H. Latifi, J. Organomet. Chem. 2016, 822,
112-117; b) S. Jammi, P. Barua, L. Rout, P. Saha, T. Punniyamurthy,
Tetrahedron Lett. 2008, 49, 1484-1487; c) V. Percec, J. Y. Bae, D. H.
Hill, J. Org. Chem. 1995, 60, 1060-1065; d) X. B. Xu, J. Liu, J. J. Zhang,
Y. W. Wang, Y. Peng, Org. Lett. 2013, 15, 550-553.
[12] K. H. V. Reddy, V. P. Reddy, J. Shankar, B. Madhav, B. S. P. A. Kumar,
Y. V. D. Nageswar, Tetrahedron Lett. 2011, 42, 2679-2682.
[13] (a) J. Krouželka, I. Linhart, Eur. J. Org. Chem. 2009, 2009, 6336-6340;
(b) A. Kumar, S. Kumar, Tetrahedron. 2014, 70, 1763-1772; (c) P. S.
Luo, F. Wang, J. H. Li, R. Y. Tang, P. Zhong, Synthesis. 2009, 2009,
921-928; (d) N. Taniguchi, Synlett. 2006, 2006, 1351-1354; (e) N.
Taniguchi, J. Org. Chem. 2007, 72, 1241-1245.
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Key topic*
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
((Insert TOC Graphic here: max.
width: 5.5 cm; max. height: 5.0 cm;
NOTE: the final letter height should
not be less than 2 mm.))
*one or two words that highlight the emphasis of the paper or the field of the study
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Nickel-catalyzed C-S coupling *
Xing Liu, Qiang Cao, Wan Xu, Meng-
Tian Zeng, Zhi-Bing Dong*
NiCl ( 5 mol% )
2
S
N
I
1
2
bpy ( 10 mol% )
1
2
+
R
R
R
R
o
S
Zn, DMF, 110 C, 18 h
S
1
17 examples
yields up to 93%
R
= H, CH , t-Bu, CF
3 3
Page No. – Page No.
2
R
= H, CH , OH, t-Bu, Cl, Br
3
Nickel-catalyzed C-S coupling:
synthesis of diarylsulfides starting
from phenyldithiocarbamates and
iodobenzenes
Text for Table of Contents
*one or two words that highlight the emphasis of the paper or the field of the study
Catalyzed by NiCl2, phenyldithiocarbamates reacted with iodobenzenes furnishing diarylsulfides smoothly with good to
excellent yields (66-93%). The protocol has the features of cheap catalyst, easy performance, broad substrate scope and nice
yields, affording an alternative way for the preparation of diarylsulfides.
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