Copper(I)-promoted trifluoromethylthiolation of arenediazonium salts with AgSCF3

Article abstract of DOI:10.1016/j.tetlet.2019.04.018

An efficient method for trifluoromethylthiolation of arenediazonium salts has been developed in mild conditions with a stable and convenient AgSCF₃. It provides a straightforward and convenient way for the synthesis of trifluoromethylthiolated compound from diazonium salts in moderate to good yields.

Full text of DOI:10.1016/j.tetlet.2019.04.018

Accepted Manuscript
Copper(I)-Promoted Trifluoromethylthiolation of Arenediazonium salts with
AgSCF3
Changge Zheng, Yang Liu, Jianquan Hong, Shuai Huang, Wei Zhang, Yupeng
Yang, Ge Fang
PII:
S0040-4039(19)30341-7
https://doi.org/10.1016/j.tetlet.2019.04.018
TETL 50733
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
4 March 2019
6 April 2019
9 April 2019
Please cite this article as: Zheng, C., Liu, Y., Hong, J., Huang, S., Zhang, W., Yang, Y., Fang, G., Copper(I)-Promoted
Trifluoromethylthiolation of Arenediazonium salts with AgSCF3, Tetrahedron Letters (2019), doi: https://doi.org/
10.1016/j.tetlet.2019.04.018
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Copper(I)-Promoted Trifluoromethylthiolation of Arenediazonium salts with AgSCF3
Changge Zhenga, , b, Yang Liua, Jianquan Honga, Shuai Huanga, Wei Zhangb, Yupeng Yanga, Ge Fangb
aKey Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu
214122, P. R. China
bSchool of Chemical Engineering, Xinjiang Agricultural University, Urumqi 830052, Xinjiang Uygur Autonomous Region, P. R. China
———
ARTICLE INFO
ABSTRACT
 Corresponding author. Tel.: +86-510-85917763; Fax: +86-510-85917763; E-mail: cgzheng@jiangnan.edu.cn (C.-G. Zheng)
† Permanent address.
Article history:
Received
Received in revised form
Accepted
An efficient method for trifluoromethylthiolation of arenediazonium salts has been developed in
mild conditions with a stable and convenient AgSCF3. It provides a straightforward and
convenient way for the synthesis of trifluoromethylthiolated compound from diazonium salts in
moderate to good yields.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Trifluoromethylthiolation
AgSCF3
Arenediazonium salts
Sandmeyer reaction
R
The compound with a aryl trifluoromethyl sulfides (ArSCF3)
structural motif have recently attracted great attention as
pharmaceuticals and agrochemicals.1 Due to the strong electron-
withdrawing effect and high lipophilicity, the trifluoromethylthio
group (SCF3) could enhance the metabolic stability and
bioavailability of the parent molecules. Since natural compounds
containing SCF3 are uncommon, it is urgently needed to develop
synthetic methodologies of trifluoromethylthio compound.2 As
the traditional method for introduction of SCF3 into aromatic
backbones, the chlorine-fluorine exchange reactions of
trihalogenomethyl thioethers usually suffer from harmful waste
and multistep synthesis under harsh reaction conditions (Scheme
1).3 Through the trifluoromethylations of sulfur-containing
substrates precursors, such as thiols,4 thiocyanates5 and
disulfides,6 these synthetic methods are limited by substrate
availability and/or functional group tolerance. By the transition
metal-catalyzed/mediated conversion of halogen7 or boric acid
substituents,8 the one-step trifluoromethylthiolation have been
carried out using easily stored, inexpensive and handled reagents
as SCF3 or CF3 sources. With nucleophilic and electrophilic
trifluoromethylthio reagents recently, direct C-H aromatic
trifluoromethylthiolation was also developed remarkably.9 The
electrophilic trifluoromethylthiolation with aryl-magnesium or
lithium reagents have been exemplified employing CF3SCl or N-
SCF3 reagents.10 The straight-forward Sandmeyer-type reaction
are potential and easy-to-handle alternatives for the
trifluoromethylthiolations, through arenediazonium salts from
cheap and broadly available aromatic amines.11
R
R
SCCl3
N2BF4
(g)
SY
(a) HF
or SbF3
Y= H
Y= CN
Y= SR
"
AgSCF
3
This work CuI,
"CF
K
2 CO
(b)
3
3
R
R
R
(g) Me4NSCF3
(c) "SCF3"
+
N2
SCF3
X
or CuSCF3
or TMSCF3,
Cu, Ni, Pd, etc.
(d)
X= Cl, Br, I
"
"SCF
3
or
Cu,
"CF
"SCF
(f)
3
"
R
R
-
3
Ag
"
(e)
SCF3
B(OH)2
MgCl
R
H
Scheme 1. Methods for aryl trifluoromethylthiolation.
Firstly reported by J. H. Clark,12 the classical Sandmeyer-type
reaction system were not suitable for the substrates of electron-
donating groups, using the expensive and unstable copper(I)
trifluoromethanethiolate (CuSCF3) (Scheme 1). Through reaction
system of CuSCN and inexpensive Ruppert-Prakash reagent
(TMSCF3) by Goossen,13, aryl trifluoromethyl thioethers are
14
exclusively formed using sodium thiocyanate (NaSCN) as a
sulfur source. With the unstable Me4NSCF3 as the
trifluoromethylthiolation reagent, the Sandmeyer-type reaction
could also be carried out in the presence of CuSCN,15 even under
condition of metal-free.16 Recently, the toxic and hard-to-get
bis(trifluoromethyl) disulfide (CF3S)2 can also be employed in
the straight-forward Sandmeyer-type trifluoromethylthiolation of
readily available arenediazonium salts, in the presence of
photocatalyst (eosin Y) by Wangelin.17 Although some important
achievements
have
been
made
in
Sandmeyer
trifluoromethylthiolation, some drawbacks are still found in these
reaction systems. For example, the trifluoromethylthiolation
reagents employed in these approaches are toxic or unstable to

2
Tetrahedron
storage for extended periods. Recently, Y. Yang and coworker
besides CH3CN. Furthermore, the reaction was carried out under
nitrogen to gain the expected product. A slightly higher yield in
air shows that the reaction proceeds can be carried through in an
easy-to-handle approach. (entry 19).
have developed a low-cost method for the preparation of CuSCF3
via triphenylphospine‐mediated deoxygenative reduction of
Langlois’ reagent (CF3SO2Na) in the presence of CuCl.7h
However, the preparation procedure is somewhat complicated
which must be carried out in high temperature under nitrogen
atmosphere. Moreover, excessive amount of triphenylphosphine
is also employed in this procedure, generating a large amount of
environmentally harmful Ph3P=O as by-product. As the relatively
inexpensive, stable and easy-to-handle reagent, AgSCF3 could
Based on the optimized reaction conditions (Table 1, Entry
12), the substrate scope of oxidative trifluoromethylthiolation for
arenediazonium salts was investigated as summarized in Table 2.
With the electron-donating substituent in aromatic ring as aryl,
alkyl, alkoxy and methylthio, the arenediazonium salt derivatives
reacted
smoothly
to
give
the
corresponding
¬
form a reactive source of SCF3 in the presence of n-Bu4NI or
trifluoromethylthiolated products (2a–2i) in reasonable yields of
58-72%. The 2-naphthyl diazonium salt was also suitable for the
reaction system to give product 2j in 60% yield. Examined the
substrate with electron-withdrawing substituent in aromatic ring,
such as halogen (1k and 1l), acetyl (1m and 1n), carbomethoxy
(1o and 1p) and cyano (1q and 1r), the arenediazonium salt
derivatives can tolerate this reaction system more efficiently with
slightly higher yields (2k-2u, 73-92%, Table 2) than the electron-
donating substituent. Comparing with aromatic substrates with in
nitro substituent in ortho (2t, 89%) and meta- (2u, 90%) position,
the pretty higher yield of the electron-withdrawing nitro in para
(2s, 92%) position indicated that electronic effect rather than
steric effects remains to be the most important influence to the
reaction system. Contrary to other SCF3 or CF3 sources, the
trifluoromethylthiolated yield of electron-deficient substrates is
overall higher than the electron-rich substrates using AgSCF3. In
addition, some arenediazonium salt derivatives, bearing pyridine
moiety (1v) and electron-withdrawing substituent, can be
converted to the corresponding trifluoromethylthiolated products
in higher yields to the reported.11-16
KI.18 Intrigued by the Sandmeyer trifluoromethylation of
aromatic amines and trifluoromethylthiolation with AgSCF3,19, 20
we have been trying to develop effective approaches for metal-
mediated trifluoromethylthiolation of arenediazonium salts with
AgSCF3.
Table 1
Optimization of the reaction conditions.a
SCF3
N2BF4
AgSCF3, Cu salt, Base, Additive
Solvent, air, rt, 12 h
Ph
Ph
2a
1a
[Cu]
2a Yield
Entry
Cu salt
Base Additive Solvent
(mmol)
0.01
0.01
0.01
0.01
0.01
0.01
0.01
(%)b
1
2
CuCl
CuBr
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
K2CO3 n-Bu4NI CH3CN
13
10
25
21
14
20
19
23
32
53
80
82
46
49
52
59
63
50
78
3
CuI
4
CuSCN
CuBr2
5
6
Cu(OAc)2
Cu(OTf)2
7
Table 2.
8
Cu(MeCN)4BF4 0.01
Trifluoromethylthiolation of Arenediazonium salts under the
9
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
0.02
0.05
0.1
optimized reaction conditions.a,b
10
11
12
13
14
15
16
17
18
19c
N2BF4
SCF3
AgSCF3, CuI, K2CO3
MeCN, air, rt, 12 h
R
R
0.1
K2CO3
-
-
-
-
-
-
-
-
CH3CN
CH3CN
CH3CN
CH3CN
DMSO
DMF
0.1
Na2CO3
2a-w
1a-w
0.1 NaHCO3
SCF3
SCF3
SCF3
SCF3
SCF3
SCF3
SCF3
SCF3
SCF3
0.1
0.1
0.1
0.1
0.1
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Ph
CH3O
2a, 70%
2f, 67%
2k, 78%
2b, 65%
2c, 60%
2d, 63%
2e, 58%
SCF3
SCF3
SCF3
NMP
CH3CN
BnO
O
CH3S
EtO
PhO
a
Reaction conditions: 1a (0.1 mmol), AgSCF3 (0.15 mmol, 1.5 equiv.),
2g, 63%
2h, 72%
2j, 60%
2i, 68%
copper salt, base (0.2 mmol, 2.0 equiv.), additive (0.2 mmol, 2.0 equiv).
solvent (1 mL), b Yields were determined by 19F NMR spectroscopy based on
1a using 4,4′-difluorobiphenyl as an internal standard. c under N2.
SCF3
SCF3
SCF3
SCF3
SCF3
SCF3
CH3O
O
Br
I
Initially, the model substrate 1a of trifluoromethylthiolation
reaction was screened to investigate the effects of different
copper salts, bases, solvents, and additives (Table 1). There is
only 13% yield of trifluoromethylthiolated product to be
obtained, using 0.01 mmol CuCl as the catalyst. Investigating
copper catalyst such as CuCl, CuBr, CuI, CuSCN, CuBr2,
Cu(OAc)2, Cu(OTf)2 and Cu(MeCN)4BF4 (entries 1–8), CuI was
suggested to be best choice for the reaction with the highest
yield. With increasement of the amount of CuCl, the improved
significantly yield of 2a show that catalytic amounts of copper
salt were insufficient to achieve high yields. Surprisingly, a
slightly higher yield of 82% was achieved in the absence of n-
Bu4NI (entry 12). Several bases such as Na2CO3, NaHCO3,
Cs2CO3 and K2CO3 were also examined to further optimize the
reaction conditions. Obviously, K2CO3 is most suitable for
achievement of corresponding product 2a in the highest yield
(entries 12–15). The influence of solvents was also investigated
in such solvents as DMSO, DMF and NMP (entries 16–18)
O
2n, 73%
2m, 81%
2o, 76%
2l, 86%
CN
SCF3
SCF3
SCF3
SCF3
NO2
C2H5O
CN
NO2
O
2p, 79%
2u, 90%
2r, 83%
2s, 92%
2q, 89%
2t, 89%
SCF3
NO2
N
2v, 76%
2w, 55%
a
Reaction conditions: 1a-1w (0.5 mmol), AgSCF3 (0.75 mmol, 1.5 equiv.),
CuI (0.5 mmol, 1.0 equiv.), K2CO3 (1.0 mmol, 2.0 equiv.), CH3CN (5 mL),
air, rt, 12 h. b Isolated yields.
Secondarily, this reaction system is feasible particularly for
large-scale applications due to its irreplaceable advantages as
easily available raw material, air insensitivity and mild reaction
conditions. To illustrate the practical application of this
transformation, the reaction was scaled up using 5 mmol of the
substrate 1s. The corresponding trifluoromethylthiolated product

2s was also obtained in isolated yield of 85% through this
reaction proceeds under the optimal conditions.
potential application of synthetic, medicinal, and agrochemical
research.
To elucidate a plausible reaction mechanism, some control
experiments were carried as shown in Table 3. Without copper
salt in the reaction system, only 10% desired product 2a was
detected. Obviously, the reactivity of metallic silver is low
without copper salt. Using 1.0 equivalents of Cu(MeCN)4BF4 as
catalyst instead of CuI, the yield of 2a was apparently declined to
40%. Added 1.0 equivalents of KI to the above reaction system,
the improved yield 78% of 2a indicated that iodine anion (I-) play
a significant role in this reaction system. As the previous
reported,21 the active species [Ag(SCF3)I]- can generate through
this reaction system with the stronger nucleophilicity than
AgSCF3. The result of the above investigation show further that
CuSCF3 species will generate on site in the presence of AgSCF3
or [Ag(SCF3)I]- with copper salt.22 Added 4.0 equivalents of the
Acknowledgments
We acknowledge the financial support for this work from the
National Natural Science Foundation of China (Nos. 21562041
and 21502070) and the Fundamental Research Funds for the
Central Universities.
References
1. (a) X.-H. Xu, K. Matsuzaki, N. Shibata, Chem. Rev. 2015, 115, 731-764.
(b) L. Chu, F.-L. Qing, Acc. Chem. Res. 2014, 47, 1513−1522;
(c) D. C. Remy, S. F. Britcher, S. W. King, P. S. Anderson, C. A. Hunt,
W. C. Randall, P. Bélanger, J. G. Atkinson, Y. Girard, C. S. Rooney, J. J.
Fuentes, J. A. Totaro, J. L. Robinson, E. A. Risley, M. Williams, J. Med.
Chem. 1983, 26, 974-980;
radical-trapping reagent
TEMPO (2,2,6,6-tetramethyl-1-
(d) B. Manteau, S. Pazenok, J.-P. Vors, F. R. Leroux, J. Fluorine Chem.
2010, 131, 140-158;
(e) V. N. Boiko, Beilstein J. Org. Chem. 2010, 6, 880-921;
(f) T. Nguyen, W.-L. Chiu, X.-Y. Wang, M. O. Sattler, J. A. Love, Org.
Lett. 2016, 18, 5492-5495;
oxylpiperidine), the reaction was obviously suppressed to give
only 8% products under the optimal conditions. It indicates that
the reaction may proceed via
a radical pathway. The
investigations of reaction temperature suggest that the yield of
product 2a decreases significantly by increase of the reaction
temperature, along with the augment of the iodobenzene as main
by-product (See the Supporting Information).
(g) P. Nikolaienko, T. Yildiz, M. Rueping, Eur. J. Org. Chem. 2016,
1091-1094.
2. (a) C. Shen, P. Zhang, Q. Sun, S. Bai, T. S. A. Hor, X. Liu, Chem. Soc.
Rev., 2015, 44, 291-314;
(b) F. Leroux, P. Jeschke, M. Schlosser, Chem. Rev. 2005, 105, 827-856;
(c) T. Liang, C. N. Neumann, T. Ritter, Angew. Chem., Int. Ed. 2013, 52,
8214-8264;
(d) A. Tlili, T. Billard, Angew. Chem., Int. Ed. 2013, 52, 6818-6819;
(e) F. Toulgoat, S. Alazet, T. Billard, Eur. J. Org. Chem. 2014, 2415-
2428.
Table 3
Control experiments.
Cu salt, KI, TEMPO
AgSCF3, K2CO3
N2BF4
SCF3
MeCN, air, rt, 12 h
Ph
Ph
3. (a) E. A. Nodiff, S. Lipschutz, P. N. Craig, M. Gordon, J. Org. Chem.
1960, 25, 60-65;
2a
1a
Entry
1a
2a
3a
4b
Cu salt
KI
-
TEMPO 2a Yield (%)c
(c) J. M. Kremsner, M. Rack, C. Pilger, C. O. Kappe, Tetrahedron Lett.
2009, 50, 3665-3668.
4. (a) C. Wakselman, M. Tordeux, J. Org. Chem. 1985, 50, 4047-4051;
(b) I. Kieltsch, P. Eisenberger, A. Togni, Angew. Chem. Int. Ed. 2007,
46, 754-757;
-
-
-
10%
40%
78%
21%
8%
Cu(MeCN)4BF4 (1.0)
Cu(MeCN)4BF4 (1.0)
CuI (1.0)
-
1.0
-
-
2.0
4.0
(c) A. Harsanyi, E. Dorko, A. Csapo, T. Bako, C. Peltz, J. Rabai, J.
Fluorine Chem. 2011, 132, 1241;
5b
CuI (1.0)
-
Reaction conditions: 1a (a 0.1 mmol, 1 equiv; b 0.5 mmol, 1 equiv.), AgSCF3
(1.5 equiv.), K2CO3 (2.0 equiv.), CH3CN (5 mL), air, rt, 12 h, Cu salt, KI, and
TEMPO (equiv.). cYield was determined by 19F NMRspectroscopy using 4,4′-
difluorobiphenyl as an internal standard.
(d) J.-J. Ma, W.-B. Yi, G.-P. Lu, C. Cai, Catal. Sci. Technol. 2016, 6,
417-421;
(e) J. J. Ma, Q. R. Liu, G. P. Lu, W. B. Yi, J. Fluorine Chem. 2017, 193,
113-117.
5. (a) T. Billard, S. Large, B.R. Langlois, Tetrahedron Lett. 1997, 38, 65-
68;
Based on the above experimental results,
a plausible
mechanism was proposed about the copper(I)-promoted
trifluoromethylthiolation process via [Ag(SCF3)I]- as shown in
Scheme 2. Firstly transferred a single electron (SET) to
arenediazonium salts 1, Cu(I) afford aryl radicals and Cu(II)
species. Then, Cu(II)SCF3 species will generate on-site quickly
through combination of Cu(II) and active species [Ag(SCF3)I]-
from the reaction of AgSCF3 and iodine anion. The desired
product 2a can achieve by aryl radicals with Cu(II)SCF3.
(b) S. Potash, S. Rozen, J. Fluor. Chem. 2014, 168, 173-176;
(c) K. Jouvin, C. Matheis, L. J. Goossen, Chem. Eur. J. 2015, 41, 14324-
14327;
(d) B. Exner, B. Bayarmagnai, F. Jia, L. J. Goossen, Chem. Eur. J. 2015,
48, 17220-17223;
(e) B. Bayarmagnai, C. Matheis, K. Jouvin, L. J. Goossen, Angew.
Chem. Int. Ed. 2015, 54, 5753-5756.
6. (a) C. Wakselman, M. Tordeux, J.-L. Clavel, B. Langlois, J. Chem. Soc.,
Chem. Commun. 1991, 993-994;
(b) B. Quiclet-Sire, R. N. Saicic, S. Z. Zard, Tetrahedron Lett. 1996, 37,
9057-9058;
(c) N. Roques, J. Fluorine Chem. 2001, 107, 311-314;
(d) G. Blond, T. Billard, B. R. Langlois, Tetrahedron Lett. 2001, 42,
2473-2475;
N2BF4
SCF3
- Cu(I)
Cu(I)
SET
Cu(II)
R
R
R
1
2
-
(e) C. Pooput, M. M´edebielle, W. R. Dolbier, Org. Lett. 2004, 6, 301-
303;
-
I
[Ag(SCF3)I]
AgSCF3
Cu(II)SCF3
(f) C. Pooput, W. R. Dolbier, M. M´edebielle, J. Org. Chem. 2006, 71,
3564-3568.
7. (a) C. Zhang, D. A. Vicic, J. Am. Chem. Soc. 2012, 134, 183-185;
(b) C. Zhang, W. W. Brennessel, D. A. Vicic, J. Fluor. Chem. 2012, 140,
112-115;
Scheme 2. Plausible mechanism.
In summary, we have developed an efficient preparation
method through copper(I)-promoted trifluoromethylthiolation for
the various arenediazonium salts, using a stable and inexpensive
AgSCF3 in moderate to good yields and mild reaction conditions.
A preliminary mechanistic investigation suggests that this
reaction process via a radical pathway. With the extensive
reaction tolerance, mild reaction condition and the easy-to-get
raw material, this method achieve a useful and practical strategy
in the synthesis of aryl trifluoromethyl sulfides, for great
(c) Z. Weng, W. He, C. Chen, R. Lee, D. Tan, Z. Lai, D. Kong, Y. Yuan,
K.-W. Huang, Angew. Chem. Int. Ed. 2013, 52, 1548-1552;
(d) W. Zhong, X. Liu, Tetrahedron Lett. 2014, 55, 4909-4911;
(e) G. Yin, I. Kalvet, F. Schönebeck, Angew. Chem. Int. Ed. 2015, 54,
6809-6813;
(f) G. Yin, I. Kalvet, U. Englert, F. Schönebeck, J. Am. Chem. Soc.
2015, 137, 4164-4172;

4
Tetrahedron
(g) P. Saravanana, P. Anbarasana, Adv. Synth. Catal. 2015, 357, 3521-
14. B. Bayarmagnai, C. Matheis, E. Risto, L. J.Goossen, Adv. Synth. Catal.
2014, 356, 2343-2348.
3528;
(h) Y. Yang, L. Xu, S. Yu, X. Liu, Y. Zhang, D. A. Vicic, Chem. Eur. J.
2016, 22, 858-863;
(i) I. Kalvet, Q. Guo, G. J. Tizzard, F. Schönebeck, ACS Catal. 2017, 7,
2126-2132.
15. C. Matheis, V. Wagner, L. J. Goossen, Chem. Eur. J. 2016, 22, 79-82.
16. G. Bertoli, B. Exner, M. V. Evers, K. Tschulik, L. Goossen, J. Fluorine
Chem. 2018, 210, 132-136.
17. D. Koziakov, M. Majek, A. Jacobi von Wangelin, Eur. J. Org. Chem.
2017, 6722-6725;
18. D. J. Adams, J. H. Clark, J. Org. Chem. 2000, 65, 1456-1460.
19. (a) G. Teverovskiy, D. S. Surry, S. L. Buchwald, Angew. Chem. Int. Ed.
2011, 50, 7312-7314;
8. (a) C. Chen, Y. Xie, L. Chu, R.-W. Wang, X. Zhang, F.-L. Qing, Angew.
Chem. Int. Ed. 2012, 51, 2492-2495;
(b) C. Chen, L. Chu, F. Qing, J. Am. Chem. Soc. 2012, 134, 12454-
12457;
(c) C. P. Zhang, D. A. Vicic, Chem. Eur. J. 2012, 7, 1756-1758;
(d) X. Shao, X. Wang, T. Yang, L. Lu, Q. Shen, Angew. Chem. Int. Ed.
2013, 52, 3457-3460;
(b) J. Xu, X. Mu, P. Chen, J. Ye, G. Liu, Org. Lett. 2014, 16, 3942-3945;
(c) W. Wu, B. Wang, X. Ji, S. Cao, Org. Chem. Front. 2017, 4, 1299-
1303.
(e) L. Zhai, Y. Li, J. Yin, K. Jin, R. Zhang, X. Fu, C. Duan, Tetrahedron
2013, 69, 10262-10266;
20. (a) Danoun, G.; Bayarmagnai, B.; Grünberg, M. F.; Goossen, L. J.
Angew. Chem., Int. Ed. 2013, 52, 7972;
(f) R. Pluta, P. Nikolaienko, M. Rueping, Angew. Chem. Int Ed. 2014,
53, 1650-1653;
(g) K. Kang, C. Xu, Q. Shen, Org. Chem. Front. 2014, 1, 294-297;
(h) Q. Glenadel, S. Alazet, A. Tlili, T. Billard, Chem. Eur. J. 2015, 21,
14694-14698;
(b) K. Zhang, X. Xu, F. Qing, J. Org. Chem. 2015, 80, 7658.
(c) J. Hong, G. Wang, L. Huo, Zheng, Chin. J. Chem. 2017, 35, 1761-
1767.
21. (a) C. Chen, X. H. Xu, B. Yang, F. Qing, Org. Lett. 2014, 16, 3372-3375;
(b) M. Jiang, F. Zhu, H. Xiang, X. Xu, L. Deng, C. Yang, Org. Biomol.
Chem. 2015, 13, 6935-6939;
(c) J. Liu, X. Xu, Z. Chen, F. Qing, Angew. Chem. Int. Ed. 2015, 54,
897-900.
22. (a) M. Hu, J. Rong, W. Miao, C. Ni, Y. Han, J. Hu, Org. Lett. 2014, 16,
2030-2033;
(i) M. Zhao, X. Zhao, P. Zheng, Y. Tian, J. Fluorine Chem. 2017, 194,
73-79;
9. (a) L. D. Tran, I. Popov, O. Daugulis, J. Am. Chem. Soc. 2012, 134,
18237-18240;
(b) A. Ferry, T. Billard, E. Bacqué, B. R. Langlois, J. Fluorine Chem.
2012, 134, 160-163.
10. (a) F. Baert, J. Colomb, T. Billard, Angew. Chem. Int. Ed. 2012, 51,
10382-10385;
(b) X. Wang, Y. Zhou, G. Ji, G. Wu, M. Li, Y. Zhang, J. Wang, Eur. J.
Org. Chem. 2014, 3093-3096.
(b) Q. Glenadel, S. Alazet, T. Billard, J. Fluorine Chem. 2015, 179, 89-
95.
Supplementary Material
11. (a) J. Wu, Y. Gu, X. Leng, Q. Shen, Angew. Chem. Int. Ed. 2015, 54,
7648–7652;
Supplementary material for this article is available online at
http://dx.doi.org/10.1016/j.tetlet.
(b) C. Matheis, B. Bayarmagnai, K. Jouvin, L. J. Goossen, : Org. Chem.
Front., 2016, 3, 3, 949-952.
(c) Y. Liu, X. Xu, F. Qing, Tetrahedron 2018, 74, 5827-5832;
12. D. J. Adams, A. Goddard, J. H. Clark, D. J. Macquarrie, Chem.
Commun. 2000, 987-988.
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13. G. Danoun, B. Bayarmagnai, M. F. Gruenberg, L. J. Goossen, Chem. Sci.
2014, 5, 1312-1316.
An efficient method with a stable and convenient AgSCF3
provides an additional way for the synthesis of
trifluoromethylthiolated compound with arenediazonium salts,
in very mild conditions and good yield.
Graphical Abstract
Copper(I)-Promoted
Leave this area blank for abstract info.
Trifluoromethylthiolation of
Arenediazonium salts with AgSCF3
Changge Zheng, Yang Liu, Jianquan Hong, Shuai Huang, Wei Zhang, Yupeng Yang and Ge Fang
N2BF4
SCF3
AgSCF3, CuI, K2CO3
MeCN, air, rt, 12 h
R
R
2a
1a
The mild reaction condition.
Highlights
•
The trifluoromethylthiolated products with
electron-withdrawing substituent were obtained in
higher yields.
The first example of the stable AgSCF3 for
trifluoromethylthiolation of arenediazonium salts.
An efficient method for trifluoromethylthiolation of
arenediazonium salts was developed.