Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis

Article abstract of DOI:10.1021/acscatal.9b04931

An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.

Full text of DOI:10.1021/acscatal.9b04931

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Letter
Dechalcogenization of Aryl Dichalcogenides To
Synthesize Aryl Chalcogenides via Copper Catalysis
Yongqiang Wang, Jie-dan Deng, Jinhong Chen, Fei Cao, Yongsheng Hou, Yuhang
Yang, Xuemei Deng, Jinru Yang, Lingxi Wu, Xiangfeng Shao, Tao Shi, and Zhen Wang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b04931 • Publication Date (Web): 06 Feb 2020
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ACS Catalysis
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Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl
Chalcogenides via Copper Catalysis
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Yongqiang Wang,†,II Jiedan Deng,†,II Jinhong Chen,† Fei Cao,‡ Yongsheng Hou,† Yuhang Yang,†
Xuemei Deng,† Jinru Yang,† Lingxi Wu,‡ Xiangfeng Shao,‡ Tao Shi,*,† and Zhen Wang*† ‡
† School of Pharmacy, Lanzhou University, West Donggang Road, No. 199, Lanzhou 730000, China
‡State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou
University, Lanzhou 730000, China
ABSTRACT: An application of dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl
chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrates scope and good
functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro and
methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and
synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder
conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling
reactions of aryl halogen are successfully accomplished with this protocol.
KEYWORDS: Aryl chalcogenides, aryl dichalcogenides, copper catalysis, dechalcogenization, organic materials
Aryl chalcogen-containing compounds have captured
widespread attention due to their essential and manifold
strategies should not be overlooked, thus alternatives are
in great need.
applications
in
biologically
active
molecules,1
Previous work:
a) Transition Metal Catalyzed Coupling Reactions
pharmaceuticals2 and organic materials.3 For instance
(Figure 1), aryl chalcogenides could be found in 5-
lipoxygenase inhibitor AZD4407,1a antitumor drug
X
S
S
Y
R2
R1
R2
R1
Axitinib,
and
organic
electronic
material
X = -Cl, -Br, -I, -NR2, -OTf,
-B(OH)2, -Sn, -ZnBr, -MgBr.
Y = -H, -SAr, -Ac, -Cl, -CN,
-NO, -NO2, -SO2R, -CN, -Bn...
triselenasumanene.3c In view of their significance
Precious metal
Poor substrates scope
Pre-functionalized sulfur
OBu
O
NH

Sensitive metallic reagent
BuO
Se
H
S
N
OBu
b) C-H Activation/Functionalization
HO
S
N
Se
O
H
S
O
S
OBu
Se
S
Y
Y
R1
R1
R2
N
R2
BuO
X
X
N
OBu
X = H, DG
Y= H, SAr
AZD4407
5-Lipoxygenase inhibitor
Axitinib
Antineoplastic
Triselenasumanene
DG is difficult to escape
Poor functional group tolerance
Electronic materials
c) Nucleophilic Substitution
Figure 1. Examples of aryl chalcogen-containing bioactive
compounds, pharmaceutical molecules and organic materials.
S
X
S
Base
R2
R1
R1
R2
X = F, Cl, Br
Only applicable for electrophilic aromatics
Y = H,TMS
in such broad fields, various methods for synthesizing aryl
sulfides have been developed,4 mainly including the
following three strategies: a) transition-metal-catalyzed
coupling5 of aryl halides, arylboronic acids or other metal
reagents with thiols, disulfides or functionalized sulfurs6
(Scheme 1a), several of these protocols use precious metal,
pre-functionalized sulfur and sensitive metallic reagent; b)
metal-catalyzed functionalization of C-H bonds,7
application and substrates scope of some of which have
been restricted for the difficulty of directing group
escaping (Scheme 1b); c) nucleophilic substitution (SNAr)
reactions,8 which are exclusively applicable for
electrophilic aromatics (Scheme 1c). Despite significant
progress has been made in aryl sulfides synthesis, the
longstanding issues existed in the above-mentioned
Poor substrates scope
This work:
R2
Y
CuI, ligand, K2CO3
Y
R2
R1
Y
R1
H2O, DMSO, 120 o
> 80 examples
C
Y = S, Se, Te
Practical and mild conditions
Applicable for organic materials with large ring tension
Wide substrates scope
Good functional group tolerance
Scheme 1. Methods for Synthesis of Aryl Sulfides
According to the previous literature, desulfurization of
aryl disulfides to hydrocarbons has been uncovered,9
whereas, selective remove of one sulfur in aryl disulfides is
challenging. At present, selective dechalcogenization of
aryl dichalcogenides en route to aryl chalcogenides is
mainly applied to synthesize organic materials with large
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Page 2 of 6
c50 µL H2O (DMSO : H2O = 20 : 1) was added. dAir was
o
ring tension, moreover, high temperature (200 - 300 C)
and excessive copper powder are required but the yield is
1
replaced by Ar. Mes. = Mesitylene; L = Ligand
2
3
4
5
6
7
8
9
10
unsatisfying.3c,
Remarkably, there is no precedent on
ensuing tested, but no enhancement on the yield was
observed. Considering the low solubility of base in DMSO,
we attempted to increase the solubility of the base by
adding water. As we predicted, the yield dramatically
jumped to 80% and the reaction time was shortened to 7h
(Table 1, entry 8; Table S3). Next, we managed to arise the
yield by screening a variety of ligands, but no satisfactory
result was presented (Table 1, entries 9 – 11; Table S4). In
the absence of CuI or base or ligand or air, no product was
detected (Table 1, entries 12 - 15), indicating the necessity
of copper salt, base, ligand and air.
dechalcogenization of ordinary aryl dichalcogenides to
ordinary aryl chalcogenides, which are important moieties
of many biological molecules. In this context, we herein
reveal
the
unprecedented
application
of
dechalcogenization of aryl dichalcogenides in synthesizing
aryl chalcogen-ides and bowl-shaped organic materials
under milder conditions.
Giving the fact that copper species could insert into C–C
bond through extrusion of CO2 to form a stable aryl-copper
intermediate in decarboxylative coupling reactions,11 we
wonder if copper salts are also amenable to show similar
effects in the extrusion of SO2. To verify our hypothesis, we
commenced our study by performing desulfurization of
1,2-di-p-tolyldisulfane (1b) in the presence of 20 mol %
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With the optimized conditions in hand, we assessed the
r e a c t i o n s c o p e w i t h v a r i o u s s y m m e t r i c a l a r y l
dichalcogenides (Scheme 2). In terms of electronical effect,
both electron-donating and electron-withdrawing
substituents at para-, meta- and ortho-positions of benzene
ring provided the desired products in good to excellent
yields (2a - 2q, 75% - 94%). In general, electron-
withdrawing groups on the phenyl ring were apt to
generate products in high yields than electron-donating
ones. As for steric hindrance effect, 2, 6-dimethylated 1r,
fused aromatic rings 1s and 1t showed good compatibility
in this reaction to give rise to the corresponding products
in good yields (2r – 2t, 80% - 85%), which suggested steric
hindrance of substrates had marginal influence on yields.
Several heterocycle disulfides were also feasible to afford
the products in good yields (2u - 2w, 76% - 82%). Of
particular note was that 4-methoxybenzyl disulfide 2x
proceeded well under standard conditions to offer the
desulfurated product in 80% yield. Some sensitive
functional groups including amide and ester were well
tolerant, providing 2y and 2z in 80% and 78% yields
r e s p e c t i v e l y . M o r e o v e r , t h e o r g a n i c s y n -
Cu(OAc)2, 40 mol
%
1,10-phenanthroline, and
3
equivalents of K2CO3 under air atmosphere at 120 oC for 24
h, and the desired product 2b was obtained in 40% yield
(Table 1, entry 1). Subsequently, optimization of the
reaction conditions was carried out by evaluating a variety
of reaction parameters. At first, copper salts were screened
and CuI was the best to generate product 2b in 48% yield
(Table 1, entries 2 – 3; Table S1). Solvents (Table 1, entries
4 – 5; Table S2) and base (Table 1, entries 6 – 7; Table S3)
were
Table 1. Optimization of The Reaction Conditionsa
Me
S
[Cu], Ligand, base,
S
S
Sol., 120 o
C
Me
Me
N
Me
1b
2b
N
N
N
N
N
Br
N
N
CuI (20 mol %), ligand (40 mol %)
Br
X
R
K2CO3 (3.0 equiv), air
L1
L2
L3
L4
X
R
R
X
DMSO, H2O, 120 o
C
R
1
2
X=S, Se, Te
entry [Cu]
sol.
base
l.
time/h yield/%b
S
S
S
S
1
Cu(OAc)2 DMSO
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
KOH
L1
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L1
L1
-
24
24
24
24
24
24
24
7
40
30
48
4
t-Bu
t-Bu
MeO
OMe
2a 82%
2b 80%
2c 82%
2d 78%
2
CuBr
CuI
CuI
CuI
CuI
CuI
CuI
CuI
DMSO
DMSO
DMF
S
S
S
S
3
BnO
OBn
Cl
Cl
Br
Cl
Br
Cl
F
F
2e 81%
2f 85%
2g 90%
2h 75%
4
MeO
S
OMe
S
S
S
5
Mes.
0
O2
N
NO2
Br
2i 90%
2j 83%
2k 78%
2l 90%
Cl
Cl
OMe
OMe
6
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
35
Trace
80
55
20
Trace
0
Br
S
S
S
S
7
2m 78%
2n 84%
2o 82%
2p 94%
8c
9c
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
-
Br
N
Br
S
S
S
S
7
2q 76%
2r 80%
2s 83%
2t 85%
10c CuI
11c CuI
7
S
N
S
S
S
S
S
S
S
N
N
7
MeO
OMe
2u 82%
2v 81%
2w 76%
2x 80%
12c
-
7
O
OMe O
S
OMe
S
S
S
13c CuI
14c CuI
15c, d CuI
7
0
HN
S
O
O
K2CO3
K2CO3
7
0
2aa 85%
2z 78%
Se
2ab 20%
Se
Te
L1
7
Trace
N
H
0%
2y 8
2ad 80%
2ae 82%
2ac 60%
aReaction conditions: 1b (0.10 mmol, 1.0 equiv), [Cu] (0.02
mmol, 20 mol %), Ligand (0.04 mmol, 40 mol %), Base (0.30
mmol, 3.0 equiv), solvent (1.0 mL), air, 120 oC. bIsolated yields.
Scheme 2. Substrates Scope of Symmetrical Aryl
Dichalcogenides.a, b aReaction conditions: 1 (0.10 mmol, 1.0
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ACS Catalysis
equiv), CuI (0.02 mmol, 20 mol %), 1,10-phenanthroline (0.04
Scheme 3. Substrates Scope of Unsymmetrical Aryl
Dichalcogenides.a, b aReaction conditions: 3/5 (0.10 mmol,
1.0 equiv), CuI (0.02 mmol, 20 mol %), 1,10-phenanthroline
(0.04 mmol, 40 mol %), K2CO3 (0.30 mmol, 3.0 equiv), DMSO:
H2O = 20 : 1, air, 120 oC. bIsolated yields.
1
2
3
4
5
6
7
8
mmol, 40 mol %), K2CO3 (0.30 mmol, 3.0 equiv), DMSO : H2O =
20 : 1, air, 120 oC. bIsolated yields.
thesis intermediates 2aa and 2ab could be obtained in
85% and 20% yields respectively. Interestingly, even
deselenization and detellurization were also successfully
achieved to produce the desirable products in moderate to
good yields (2ac: 60%; 2ad: 80%; 2ae: 82%).
derived from 4-methoxyphenyl and several 4-substituted
phenyls (3l - 3p). Additionally, unsymmetrical aryl
disulfides created from the combination of 3-
methoxyphenyls (3q - 3u) or 2-methoxyphenyls (3v - 3z)
with several 4-substituted phenyls were compatible in this
transformation to provide 4q - 4z in good yields (65% -
78%); unsymmetrical aryl disulfides originated from 2-
methyl benzoate and several 4-substituted phenyls (3aa -
3ad) proceeded well to allow access to the expected
products in good yields as well (4aa - 4ad, 70% - 75%).
Significantly, several more complicated molecules (4ae -
4ah) were obtained in moderate yields, and various
functional groups such as alkenyl (4ai), methylsulfonyl
(4aj), aldehyde (4ak), ketone (4al) and nitrile (4am) were
all tolerant in this reaction. Overall, this protocol provides
a convenient way to synthesize various unsymmetrical aryl
sulfides.
Next, we further assessed the scope of unsymmetrical
aryl disulfides (Scheme 3a). Desulfuration of 3a - 3k
bearing an electron-withdrawing group (-F, -Cl -Br) or an
electron-donating group (Me) on ortho, mate or para-
position of benzene ring provided 4a - 4k in moderate to
good yields (60% - 80%), and similar results (4l - 4p, 65%
-73%) were disclosed when using unsymmetrical aryl
disulfides
9
10
11
12
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a). Substrates scope of unsymmetrical aryl disulfides
CuI (20 mol %), ligand (40 mol %)
S
R2
K2CO3 (3.0 equiv), air
R1
R2
S
S
R1
DMSO, H2O, 120 o
C
4
3
F
Cl
t-Bu
S
S
S
S
MeO
MeO
4b 64%
MeO
MeO
MeO
4a 60%
MeO
Br
4d 68%
4c 70%
Having obtained many symmetrical and unsymmetrical
chalcogenides by dechalcogenization, we wondered if
there was any preference between desulfuration and
deselenization, thus dechalcogenization of a series of
selanylsulfanes were examined (Scheme 3b). To our
surprise, when we exploited (4-methoxyphenyl)
(phenylselanyl)sulfane 5a as the starting material, the
desulfurization product 6a was obtained in 63% yield.
However, the deselenization product was too little to
obtain but only permitted to be observed in GC-MS.
Subsequently, several selanylsulfanes were tested and all
examples provided desulfuration products 6b - 6f in
moderate to good yields (60 - 78%). This transformation
affords a feasible alternative to remove sulfur, where both
sulfur and selenium existed in one compound.
S
S
Br
S
Cl
MeO
S
MeO
4g 78%
4h 68%
4f 60%
4e 70%
S
S
S
S
MeO
Cl
Br
MeO
MeO
MeO
4l 72%
4k 74%
4j 80%
4i 65%
S
S
S
S
MeO
Br
MeO
MeO
Cl
F
MeO
MeO
F
MeO
4m 65%
4n 72%
4o 73%
4p 68%
MeO
S
S
S
MeO
S
Cl
4t 74%
4r 65%
4s 73%
4q 68%
OMe
OMe
OMe
MeO
S
S
S
S
Br
F
4u 70%
4v 77%
4x 78%
CO2Me
4w 76%
The robustness of this method was shown by the late-
stage modification of biological molecule and synthesis of
pharmaceutical (Scheme 4). Estrone as an estrogen
secreted by human and animals, was modified by
desulfuration of 7 under our optimal conditions and
rendered aryl sulfide 8 in 55% yield. Subsequently,
vortioxetine as a new medicine for treating depression was
also synthesized. Starting from disulfide 9, the key
precursor 10 was synthesized using our protocol, which
then could be trans-formed into vortioxetine via
palladium-catalyzed Buchwald-Hartwig cross coupling12
and deprotection of amine13 in 63% yield for two steps.
OMe
OMe
CO2Me
S
S
S
S
Br
Cl
4aa 70%
4ab 72%
4y 75%
4z 68%
CO2Me
CO2Me
S
S
S
S
S
F
Br
4ad 70%
4ac 75%
4af 67%
4ae 68%
S
S
S
N
4ai 65%
4ah 70%
4ag 68%
S
S
S
Encouraged by the above outcomes, our method was
further extended for synthesis of more challenging bowl-
shaped organic materials with great ring tension (Scheme
5).3c Deselenization of 11 was achieved with 12 obtained
S
O
H
O
Me
S
NC
Me
O
O
4aj 75%
4ak 65%
4al 68%
4am 73%
b). Substrates scope of unsymmetrical aryl diselenides
CuI (20 mol %), ligand (40 mol %)
Se
K2CO3 (3.0 equiv), air
S
R
Se
DMSO, H2O, 120 o
C
R
5
6
CO2Me
6a
6b
6c
R=4-OMe, 63%
R=3-OMe, 60%
R=2-OMe, 64%
Se
Se
Ph
Se
R
Se
O2N
MeO
6d 70%
6e 72%
6f 78%
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Page 4 of 6
O
(a)
O
S
H
Standard Conditions
TEMPO
1
2
3
4
5
6
Standard conditions
S
S
N
H
S
Me
O
H
H
55%
S
H
H
S
S
1b
1b' 70%
2b 0%
Me
7
8
(b)
H
S
S
N
O
Br
S
Me
Br
Standard
conditions
Standard Conditions
Me
S
a, b
S
S
Me
N
O
S
63%
63% for two steps
S
16
2b 8%
17 70%
Me
Me
7
8
9
Me
9
10
Vortioxetine
Scheme 6. Control Experiments
Scheme 4. Modification of Estrone and Synthesis of
Vortioxetine. a. Pd2(dba)3 (2.5 mol %), BINAP (10 mol %), t-
BuONa (1.4 equiv), toluene, 100 C, tert-butyl piperazine-1-
In conclusion, we revealed an unprecedented
dechalcogenization of aryl dichalcogenides via copper
catalysis for the synthesis of aryl chalcogenides in
moderate to excellent yields, using simple and accessible
aryl dichalcogenides as starting materials rather than
odorous thiophenols. This approach featured the practical
conditions, broad substrates scope and excellent functional
group tolerance, even compatible with several sensitive
groups such as aldehyde, ketone, ester, amide, cyanide,
alkene, nitro and methylsulfonyl. Moreover, the robustness
of this strategy was confirmed by successful modification
of estrone and synthesis of vortioxetine. There are two
innovations of this work which are over the previously
reported synthetic methods of diaryl sulfides using metal-
catalyzed C-S coupling reactions: 1) one is this protocol
could be served as an important and new supplementary
method for synthesis of diaryl sulfides, especially for the
synthesis of challenging bowl-shaped organic materials
with great ring tension and for the synthesis of some
halogen contained diaryl sulfides which could not be
synthesized by using metal-catalyzed coupling reactions of
aryl halogen with sulfur sources; 2) the other one is this
transformation affords a feasible alternative to remove
sulfur, where both sulfur and selenium atoms existed in
one compound. The powerful strategy holds a promise to
apply in biological sulfur-containing lead compound
discovery, sulfur-containing medicine and functional
organic materials synthesis. Related works are under way
in our laboratory.
10
11
12
13
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o
carboxylate (1.2 equiv). b. TFA, DCM, R.T., 63% over two
steps.
in 95% yield. Then desulfurization of 13 was explored and
afforded 15 in 40% yield, along with 20% of 14, which
could be further transformed into 15 by desulfurization. In
lieu of a large amount of copper powder and high
temperature needed in previous reports, catalytic amount
of CuI and a lower reaction temperature were used in our
protocol, this milder condition provides a new way for
synthesis of these chalcogenides-containing organic
materials.
OBu
OBu
BuO
BuO
Se
Se
OBu
OBu
OBu
OBu
a
Se
Se
95%
Se
Se
BuO
BuO
Se
BuO
BuO
OBu
OBu
OBu
OBu
11
12
OBu
OBu
S
S
S
BuO
S
S
S
OBu
OBu
OBu
OBu
OBu
OBu
b
S
S
S
14
15
20% for
40% for
S
S
S
BuO
BuO
BuO
13
14
15
OBu
OBu
a
55%
Scheme 5. Synthesis of Triselenasumanene 12 and
Trithiasumanene 15. a. CuI (20 mol %), 1,10-
phenanthroline (40 mol %), K2CO3 (3.0 equiv), DMSO : H2O =
ASSOCIATED CONTENT
o
20 : 1, air, 160 C. b. CuI (40 mol %), 1,10-phenanthroline (80
mol %), K2CO3 (6.0 equiv), DMSO : H2O = 20 : 1, air, 160 oC.
Supporting Information
The Supporting Information is available free of charge on the
To dig in on the mechanism details, two control
experiments were designed and conducted. When TEMPO
was added to the reaction system, the 2,2,6,6-tetramethyl-
1-((p-tolylthio)oxy)piperidine 1b′ was obtained (Scheme
6a) and the desired product 2b was not observed at all,
depicting this protocol might involve a radical process.
Subsequently, S-p-tolyl benzenesulfonothioate (16) was
prepared and employed in this reaction, to our delight, the
resulting product 17 was obtained in 70% yield, along
with 2b in 8% yield, which demonstrated that compound
16 may be the intermediate of this reaction (Scheme 6b).
The plausible mechanism is shown in Supporting
Information (Scheme S1) and further detailed studies are
still required to verify.
ACS
Publications
website.
Synthetic procedures, characterization data and spectra of
compounds, and other additional data (PDF)
AUTHOR INFORMATIO
Corresponding Author
shit18@lzu.edu.cn; zhenw@lzu.edu.cn
ORCID
Tao Shi: 0000-0003-4118-8022
Zhen Wang: 0000-0003-4134-1779
Author ContributionsII
Y. W. and J. D. contributed equally.
Notes
The authors declare no competing financial interest.
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[5] For transition metal-catalyzed coupling reactions of aryl
ACKNOWLEDGMENT
halides, arylboronic acids or other metal reagents with thiols and
disulfides, please see: (a) Cheng, J.-H.; Ramesh, C.; Kao, H.-L.;
Wang, Y.-J.; Chan, C.-C.; Lee, C.-F. Synthesis of Aryl Thioethers
through the N-Chlorosuccinimide-Promoted Cross-Coupling
Reaction of Thiols with Grignard Reagents. J. Org. Chem. 2012, 77,
10369-10374. (b) Johnson, M. W.; Hannoun, K. I.; Tan, Y.; Fu, G. C.;
Peters, J. C. A Mechanistic Investigation of the Photoinduced,
Copper-mediated Cross-Coupling of an Aryl Thiol with an Aryl
Halide. Chem. Sci. 2016, 7, 4091-4100. (c) Tber, Z.; Hiebel, M. A.; El
Hakmaoui, A.; Akssira, M.; Guillaumet, G.; Berteina-Raboin, S. Fe–
Cu Catalyzed Synthesis of Symmetrical and Unsymmetrical Diaryl
Thioethers Using 1,3-benzoxazole-2-thiol As A Sulfur Surrogate.
RSC Adv. 2016, 6, 72030-72036. (d) Jiang, M.; Li, H.; Yang, H.; Fu,
H. Room-Temperature Arylation of Thiols: Breakthrough with
Aryl Chlorides. Angew. Chem. Int. Ed. 2017, 56, 874-879. (e) Wang,
L.; Xie, Y.; Huang, N.; Zhang, N.; Li, D.; Hu, Y.; Liu, M.; Li, D.
Disulfide-Directed C–H Hydroxylation for Synthesis of Sulfonyl
Diphenyl Sulfides and 2-(Phenylthio)phenols with Oxygen as
Oxidant. Adv. Synth. Catal. 2017, 359, 779-785. (f) Dong, Z.;
Balkenhohl, M.; Tan, E.; Knochel, P. Synthesis of Functionalized
Diaryl Sulfides by Cobalt-Catalyzed Coupling between Arylzinc
Pivalates and Diaryl Disulfides. Org. Lett. 2018, 20, 7581-7584.
(g) Jones, K. D.; Power, D. J.; Bierer, D.; Gericke, K. M.; Stewart, S. G.
Nickel Phosphite/Phosphine-Catalyzed C–S Cross-Coupling of
Aryl Chlorides and Thiols. Org. Lett. 2018, 20, 208-211. (h) Shieh,
Y.-C.; Du, K.; Basha, R. S.; Xue, Y.-J.; Shih, B.-H.; Li, L.; Lee, C.-F.
Syntheses of Thioethers and Selenide Ethers from Anilines. J. Org.
Chem. 2019, 84, 6223-6231.
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2
3
4
5
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7
8
This manuscript is dedicated to Lanzhou University on the
occasion of its 110th birthday. We are especially grateful to
Prof. Zhaoqing Xu for helpful discussions on mechanism study.
Financial support was provided by the Recruitment Program
of Global Experts (1000 Talents Plan) and the Fundamental
Research Funds for the Central Universities (lzujbky-2019-
ct08).
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