Tandem trifluoromethylthiolation/aryl migration of aryl alkynoates to trifluoromethylthiolated alkenes

Article abstract of DOI:10.1039/c7cc06232j

A trifluoromethylthiolation initiated aryl migration of aryl alkynoates was disclosed. This protocol employs AgSCF₃ as the SCF₃ source and MeCN as both the solvent and the hydrogen source. This provides a new access to trifluoromethylthiolated alkenes from readily available substrates and reagents.

Full text of DOI:10.1039/c7cc06232j

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
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Tandem Trifluoromethylthiolation/Aryl Migration of Aryl
Alkynoates to Trifluoromethylthiolated Alkenes
Huan Li,a Shuai Liu,a Yangen Huang,a Xiu-Hua Xub and Feng-Ling Qing*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
trifluoromethylthiolation initiated aryl migration of aryl
alkynoates was disclosed. This protocol employs AgSCF3 as the
SCF3 source and MeCN as both the solvent and the hydrogen
source. It provides a new access to trifluoromethylthiolated
alkenes from readily available substrates and reagents.
In the past few years, the trifluoromethylthio group (SCF3) has
experienced a strong acceleration of interest.1 This renewed
interest apparently is stimulated by the strong electron-
withdrawing power and extremely high lipophilicity of SCF3
group.2 The development of new trifluoromethylthiolating
reagents3 and new (C─H,4 C─B,5 C─N,6 C─O7 and C─X (X = Cl, Br,
I)8) trifluoromethylthiolation reactions have provided sought-
after strategies for the preparation of SCF3-containing
compounds. However, most of the recent research interests
are focused on the preparation of trifluoromethylthiolated
arenes, alkynes, and alkanes. Methods for the synthesis of
trifluoromethylthiolated alkenes are limited.
Normally, trifluoromethylthiolated alkenes are prepared by
transition-metal-mediated/catalyzed trifluoromethylthiolation
of vinyl boronic acids, vinyl halides or vinyl triflates.3b,3e,5b,5f,8f,9
Recently, the C─H trifluoromethylthiolation of alkenes has
been reported by Glorius10 and Shen,3m respectively. Very
Scheme 1 Methods for the preparation of trifluoromethylthiolated
alkenes from alkynes.
trifluoromethylthiolating reagent under BF3·Et2O activation
(Scheme 1a).12a Recently, Zhao reported a selenide-catalyzed
regio- and stereoselective difunctionalization of alkynes to
afford trifluoromethylthiolated alkenyl triflates and arenes
(Scheme 1b).12b The anti-Markovnikov- and Markovnikov-
selective hydrotrifluoromethylthiolation of terminal alkynes
was developed by Cao and co-workers (Scheme 1c).12c Very
recently, the stereoselective bis-trifluoromethylthiolation of
alkynes were respectively reported by Tlili and Billard (Scheme
1d)12d as well as our group (Scheme 1e)12e. In continuation of
recently,
our
group
disclosed
a
decarboxylative
trifluoromethylthiolation of cinnamic acids for the preparation
of trifluoromethylthiolated alkenes.11 Besides the above
trifluoromethylthiolation of vinyl substrates, the addition of
SCF3 group to alkynes has also been explored as alternative
approaches to trifluoromethylthiolated alkenes.12,13 For
example,
Billard
and
co-workers
disclosed
the
oxytrifluoromethylthiolation of alkynes with electrophilic
a.College of Chemistry, Chemical Engineering and Biotechnology, Donghua
University, 2999 North Renmin Lu, Shanghai 201620, China
E-mail: flq@mail.sioc.ac.cn
our
research
interest
in
difunctionalization-type
fluoroalkylation reactions,12e,14 herein we describe a tandem
trifluoromethylthiolation/aryl migration of aryl alkynoates with
AgSCF3 (Scheme 1f). This protocol provides a new access to
trifluoromethylthiolated alkenes.
b.Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Science, 345 Lingling Lu, Shanghai 200032, China
Electronic supplementary information (ESI) available: Detailed experimental
†
procedures, and analytical
DOI: 10.1039/x0xx00000x
data
for all
new compounds. See
Aryl alkynoates are easily available building blocks for the
preparation of various 3-functionalized coumarins via cascade
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cyclization.15
For
example,
the
Table 2. Substrate scope of trifluoromethylthiolation of aryl
intramolecular
alkynoatesa
trifluoromethylation, carboethoxydifluoromethylation, and
trifluoromethylthiolation of aryl alkynoates have been
reported by the groups of Lu&Ding,15b Fu,15e and Wang13g for
the preparation of the corresponding fluorinated coumarins.
During the investigation of the reaction mechanism of bis-
trifluoromethylthiolation of alkynes,12e it was interesting to
find that the reaction of 3-phenylpropiolate (1a) and AgSCF3 in
the presence of Na2S2O8 in MeCN at 80 oC afforded
trifluoromethylthiolated coumarin (2a) as the minor product
and trifluoromethylthiolated alkene (3a) as the major product
(Table 1, entry 1). This result was in striking contrast to the
reported trifluoromethylthiolation/cyclization of 1a in
DMSO,13g which gave 2a as the major product (entry 2).
Intrigued by the above results, we then optimized the
reaction conditions to improve the yield of 3a. To explore the
unique effect of solvents to this reaction, other solvents, such
as DMF, acetone, MeNO2, and PhCN, were examined, but
neither higher yield nor better chemoselectivity was obtained
(entries 3-6). Further investigation of the reaction temperature
revealed that 100 oC was optimal, giving 3a in 65% yield
(entries 7-9). Subsequently, switching the oxidant from
Na2S2O8 to K2S2O8 or (NH4)2S2O8 could not give better results
(entries 10 and 11). Finally, different additives including copper
salts (CuSO4 and CuI) and hydrogen sources (1,4-CHD and
Et3SiH) were investigated (entries 12-15). However, the yield of
3a was not improved.
Table 1. Optimization of reaction conditionsa
aReaction conditions: 1 (0.2 mmol), AgSCF3 (0.5 mmol), Na2S2O8 (0.5 mmol),
MeCN (4.0 mL), 100 oC, under N2, 2 h, isolated yields.
Entry Oxidant
Additive Solvent
Temperature Yield (2a/3a, %)b
With the optimized conditions in hand, we then explored
the scope of this tandem trifluoromethylthiolation/aryl
migration reaction. As shown in Table 2, various aryl
1
2
3
4
5
6
7
8
Na2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
―
―
―
―
―
―
―
―
MeCN
DMSO
DMF
80 oC
80 oC
80 oC
8/44
81/5
10/8
Acetone 80 oC
trace/0
0/0
alkynoates
1
underwent this transformation to afford the
in moderate
MeNO2
PhCN
80 oC
corresponding trifluoromethylthiolated alkenes
3
80 oC
0/0
to good yields. Diaryl alkynoates with either electron-donating
or electron-withdrawing substituents on both of the benzene
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
60 oC
trace/38
6/65
100 oC
120 oC
100 oC
100 oC
100 oC
100 oC
100 oC
100 oC
rings (1b
Substrates with different substituents, such as alkyl (1g and
1h), methoxy (1i), halogen (1j ), nitro (1m), nitrile (1n), and
-f) reacted smoothly to give the desired products.
9
Na2S2O8
K2S2O8
―
trace/33
8/61
10
11
12
13
14
15
―
–
l
(NH4)2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
Na2S2O8
―
6/53
ester (1o), on the benzene ring attached onto the triple bond
were all compatible under the standard conditions. Noticeably,
the reaction was also workable when a thiophenyl group was
substituted on the alkyne (1p). Finally, different substituents on
CuSO4
CuI
trace/49
0/0
1,4-CHD MeCN
Et3SiH MeCN
trace/trace
trace/trace
the phenoxy ring (1q
-
t
)
also showed high tolerance under
in good yields. It is
aReaction conditions: 1a (0.1 mmol), AgSCF3 (0.25 mmol), oxidant (0.25
mmol), additive (0.1 mmol), solvent (2.0 mL), temperature, under N2, 2 h.
bYields determined by 19F NMR spectroscopy using trifluoromethylbenzene
as an internal standard.
standard conditions, affording products 3q
-t
worth mentioning that substrate 1u with two methyl groups
substituted at the ortho-position of the phenoxy ring gave the
2 | J. Name., 2012, 00, 1-3
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desired product 3u in 21% yield, probably due to the steric 1,4-aryl migration on an ester moiety, followed by decarboxylation
hindrance.
of carboxyl radical
abstracts hydrogen from MeCN to afford the desired
. Alternatively, vinyl radical might undergo 6-endo
Addition of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), a cyclization/oxidation/deprotonation processes to give
C yields the vinyl radical D. Finally, the radical
To gain insights into the reaction mechanism, preliminary
D
mechanistic experiments were carried out (Scheme 2). products
3
A
well-known free radical scavenger, to the standard reaction trifluoromethylthiolated coumarins 2 as the major product in
conditions of 1a could significantly inhibit the formation of DMSO.13g The better solubility of Na2S2O8 in DMSO than that in
desired product 3a (Scheme 2a), which indicated that a radical MeCN might accelerate the oxidation of radical intermediate E to
pathway was probably involved in this reaction. Furthermore, cation intermediate F, thus providing 2 as the major product.
several deuterium-labeling experiments were performed to However, it is not clear how exactly the solvents affect the
elucidate the hydrogen source of trifluoromethylthiolated chemoselectivity in this reaction at the moment.
alkenes (Scheme 2b). The reaction in MeCN/D2O gave 3a in In conclusion, we have developed
35% yield. No deuterated product 4a was detected by 19F NMR trifluoromethylthiolated
alkenes
a
new approach to
by oxidative
or GC-MS. 4a was formed in MeCN/CD3CN or CD3CN (see the trifluoromethylthiolation of aryl alkynoates with AgSCF3. Primary
supporting information), These results showed that MeCN mechanistic investigations revealed that this reaction proceeds
served as the hydrogen atom source in this reaction. As silver through a radical trifluoromethylthiolation-initiated aryl migration
(I) trifluoromethanethiolate was prepared from the reaction of process. Further explorations of the reaction mechanism and other
AgF and CS2 in CH3CN, the exact molecular formula of
silver tandem fluoroalkylation/migration reactions are in progress in our
(I) trifluoromethanethiolate is 3AgSCF3⋅
in the formation of compound 3a when CD3CN was used as the
CH3CN.4i This resulted laboratory.
We thank the National Natural Science Foundation of China
(21332010, 21421002), the Strategic Priority Research Program of
the Chinese Academy of Sciences (XDB20000000), Youth Innovation
solvent.
On the basis of the results above and previous reports,16
a
plausible reaction mechanism is depicted in Scheme 3. Initially, Promotion Association CAS (No. 2016234), and Shanghai Pujiang
AgSCF3 is oxidized by Na2S2O8 to furnish the SCF3 radical via Program (No. 15PJ1410300) for financial support.
AgIISCF3.4h,4i,17 Then, the addition of SCF3 radical to aryl
alkynoates 1 generates intermediate A, which could undergo
ipsocyclization to give the spiro intermediate B 16
Notes and references
.
Subsequently,
1 For recent reviews, see: (a) F. Toulgoat, S. Alazet and T.
Billard, Eur. J. Org. Chem., 2014, 2415; (b) L. Chu and F.-
L. Qing, Acc. Chem. Res., 2014, 47, 1513; (c) X. Shao, C.
Xu, L. Lu and Q. Shen, Acc. Chem. Res., 2015, 48, 1227;
(d) X.-H. Xu, K. Matsuzaki and N. Shibata, Chem. Rev.,
2015, 115, 731; (e) H. Chachignon and D. Cahard, Chin.
J. Chem., 2016, 34, 445; (f) S. Barata-Vallejo, S. Bonesi
and A. Postigo, Org. Biomol. Chem., 2016, 14, 7150; (g)
H. Zheng, Y. Huang and Z. Weng, Tetrahedron Lett.,
2016, 57, 1397.
2 (a) A. Leo, C. Hansch and D. Elkins, Chem. Rev., 1971, 71
525; (b) C. Hansch, A. Leo and R. W. Taft, Chem. Rev.,
1991, 91 165; (c) F. Leroux, P. Jeschke and M.
,
,
Schlosser, Chem. Rev., 2005, 105, 827; (d) B. Manteau,
S. Pazenok, J. P. Vors and F. R. Leroux, J. Fluorine Chem.,
2010, 131, 140.
Scheme 2 Mechanistic investigation.
3 (a) Z. Weng, W. He, C. Chen, R. Lee, D. Tan, Z. Lai, D. Kong,
Y. Yuan and K.-W. Huang, Angew. Chem., Int. Ed., 2013,
52, 1548; (b) X. Shao, X. Q. Wang, T. Yang, L. Lu and Q.
Shen, Angew. Chem., Int. Ed., 2013, 52, 3457; (c) Y.-D.
Yang, A. Azuma, E. Tokunaga, M. Yamasaki, M. Shiro
and N. Shibata, J. Am. Chem. Soc., 2013, 135, 8782; (d)
S.-G. Li and S. Zard, Org. Lett., 2013, 15, 5898; (e) R.
Pluta, P. Nikolaienko and M. Rueping, Angew. Chem.,
Int. Ed., 2014, 53, 1650; (f) E. V. Vinogradova, P. Müller
Ar
O
SCF3
Na2S2O8
O
AgSCF3
+
CH3CN
H
Ar
1
3
S2O82-
AgIISCF3
CH3CN
SCF3
Ar
CF3SSCF3
SCF3
D
CO2
Ar
and S. L. Buchwald, Angew. Chem., Int. Ed., 2014, 53
,
Ar
SCF3
O
Ar
SCF3
O
3125; (g) C. Xu, B. Ma and Q. Shen, Angew. Chem., Int.
Ed., 2014, 53, 9316; (h) S. Alazet, L. Zimmer and T.
Billard, Chem. Eur. J., 2014, 20, 8589; (i) L. Jiang, J. Qian,
W. Yi, G. Lu, C. Cai and W. Zhang, Angew. Chem., Int.
Ed., 2015, 54, 14965; (j) X. Shao, C. Xu, L. Lu and Q.
Shen, J. Org. Chem., 2015, 80, 3012; (k) Y. Yang, L. Xu, S.
Yu, X. Liu, Y. Zhang and D. A. Vicic, Chem. Eur. J., 2016,
SCF3
O
COO
O
A
B
C
Ar
Ar
Ar
H
H
SCF3
O
SCF3
O
SCF3
O
- H+
[O]
+
22
Tokunaga, X. Li and N. Shibata, ChemistryOpen, 2016,
188; (m) P. Zhang, M. Li, X.-S. Xue, C. Xu, Q. Zhao, Y. Liu,
, 858; (l) Z. Huang, K. Okuyama, C. Wang, E.
O
O
O
5
,
E
F
2
Scheme 3 Proposed reaction mechanism.
This journal is © The Royal Society of Chemistry 20xx
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H. Wang, Y. Guo, L. Lu and Q. Shen, J. Org. Chem., 2016,
Journal Name
9 (a) Y. Huang, J. Ding, C. Wu, H. Zheng and Z. Weng, J. Org.
Chem., 2015, 80, 2912; (b) A. B. Dürr, G. Yin, I. Kalvet, F.
Napoly and F. Schoenebeck, Chem. Sci., 2016, 7, 1076.
81, 7486; (n) H. Chachignon, M. Maeno, H. Kondo, N.
Shibata and D. Cahard, Org. Lett., 2016, 18, 2467.
4 For selected examples, see: (a) C. Chen, L. Chu and F.-L.
Qing, J. Am. Chem. Soc., 2012, 134, 12454; (b) L. D.
Tran, I. Popov and O. Daugulis, J. Am. Chem. Soc., 2012,
134, 18237; (c) S. Alazet, L. Zimmer and T. Billard,
10R. Honeker, R. A. Garza-Sanchez, M. N. Hopkinson and F.
Glorius, Chem. Eur. J., 2016, 22, 4395.
11S. Pan, Y. Huang and F.-L. Qing, Chem. Asian J., 2016, 11
2854.
,
Angew. Chem., Int. Ed., 2013, 52
,
10814; (d) T.
12(a) A. Ferry, T. Billard, B. R. Langlois and E. Bacqué,
Angew. Chem., Int. Ed., 2009, 48, 8551; (b) J.-J. Wu, J.
Xu and X. Zhao, Chem. Eur. J., 2016, 22, 15265; (c) W.
Wu, W. Dai, X. Ji and S. Cao, Org. Lett., 2016, 18, 2918;
(d) A. Tlili, S. Alazet, Q. Glenadel and T. Billard, Chem.
Eur. J., 2016, 22, 10230; (e) S. Pan, H. Li, Y. Huang, X.-H.
Xu and F.-L. Qing, Org. Lett., 2017, 19, 3247.
13For the preparation of SCF3-containing cyclic compounds
from alkynes, see: (a) Q. Xiao, J. Sheng, Z. Chen and J.
Wu, Chem. Commun., 2013, 49, 8647; (b) Q. Xiao, H.
Bootwicha, X. Liu, R. Pluta, I. Atodiresei and M. Rueping,
Angew. Chem., Int. Ed., 2013, 52, 12856; (e) X. Wang, T.
Yang, X. Cheng and Q. Shen, Angew. Chem., Int. Ed.,
2013, 52, 12860; (f) C. Xu and Q. Shen, Org. Lett., 2014,
16, 2046; (g) C. Chen, X.-H. Xu, B. Yang and F.-L. Qing,
Org. Lett., 2014, 16, 3372; (h) S. Guo, X. Zhang and P.
Tang, Angew. Chem., Int. Ed., 2015, 54, 4065; (i) H. Wu,
Z. Xiao, J. Wu, Y. Guo, J.-C, Xiao, C. Liu and Q.-Y. Chen,
Angew. Chem., Int. Ed., 2015, 54, 4070; (j) H.-Y. Xiong, T.
Besset, D. Cahard and X. Pannecoucke, J. Org. Chem.,
2015, 80, 4204.
Zhu, G. Li and Z. Chen, Adv. Synth. Catal., 2014, 356
,
3809; (c) J. Sheng, S. Li and J. Wu, Chem. Commun.,
2014, 50, 578; (d) J. Sheng, C. Fan and J. Wu, Chem.
Commun., 2014, 50, 5494; (e) Y. Li, G. Li and Q. Ding,
Eur. J. Org. Chem., 2014, 5017; (f) D.-Q. Chen, P. Gao,
P.-X. Zhou, X.-R. Song, Y.-F. Qiu, X.-Y. Liu and Y.-M.
Liang, Chem. Commun., 2015, 51, 6637; (g) Y.-F. Zeng,
D.-H. Tan, Y. Chen, W.-X. Lv, X.-G. Liu, Q. Li and H.
5 (a) C. Chen, Y. Xie, L. Chu, R.-W. Wang, X. Zhang and F.-L.
Qing, Angew. Chem., Int. Ed., 2012, 51, 2492; (b) C.-P.
Zhang and D. A. Vicic, Chem. Asian J., 2012, 7, 1756; (c)
L. Zhai, Y. Li, J. Yin, K. Jin, R. Zhang, X. Fu and C. Duan,
Tetrahedron, 2013, 69, 10262; (d) K. Kang, C. Xu and Q.
Shen, Org. Chem. Front., 2014, 1, 294; (e) X. Shao, T. Liu,
L. Lu and Q. Shen, Org. Lett., 2014, 16, 4738; (f) Q.
Glenadel, S. Alazet, A. Tlili and T. Billard, Chem. Eur. J.,
2015, 21, 14694; (g) S. R. Dubbaka, A. R. Atthunuri, K. C.
Prakash, P. Rangabashyam, S. Gadde and R.
Kothandaraman, Synthesis, 2016, 48, 1246.
Wang, Org. Chem. Front., 2015, 2, 1511; (h) Y.-F. Qiu,
X.-Y. Zhu, Y.-X. Li, Y.-T. He, F. Yang, J. Wang, H.-L. Hua, L.
Zheng, L.-C. Wang, X.-Y. Liu and Y.-M. Liang, Org. Lett.,
2015, 17, 3694; (i) Y.-F. Qiu, X.-R. Song, M. Li, X.-Y. Zhu,
A.-Q. Wang, F. Yang, Y.-P. Han, H.-R. Zhang, D.-P. Jin, Y.-
X. Li and Y.-M. Liang, Org. Lett., 2016, 18, 1514; (j) D.-P.
Jin, P. Gao, D.-Q. Chen, S. Chen, J. Wang, X.-Y. Liu and
Y.-M. Liang, Org. Lett., 2016, 18, 3486; (k) Y.-K. Song,
P.-C. Qian, F. Chen, C.-L. Deng and X.-G. Zhang,
Tetrahedron, 2016, 72, 7589.
6 (a) B. Bayarmagnai, C. Matheis, E. Risto and L. J. Goossen,
Adv. Synth. Catal., 2014, 356, 2343; (b) Q. Lefebvre, E.
Fava, P. Nikolaienko and M. Rueping, Chem. Commun.,
2014, 50, 6617; (c) G. Danoun, B. Bayarmagnai, M. F.
Gruenberg and L. J. Goossen, Chem. Sci., 2014, 5, 1312;
(d) X. Wang, Y. Zhou, G. Ji, G. Wu, M. Li, Y. Zhang and J.
Wang, Eur. J. Org. Chem., 2014, 3093; (e) M. Hu, J.
Rong, W. Miao, C. Ni, Y. Han and J. Hu, Org. Lett., 2014,
16, 2030; (f) E. Emer, J. Twilton, M. Tredwell, S.
Calderwood, T. L. Collier, B. Liégault, M. Taillefer and V.
Gouverneur, Org. Lett., 2014, 16, 6004; (g) C. Matheis,
V. Wagner and L. J. Goossen, Chem. Eur. J., 2016, 22, 79;
(h) C. Matheis, T. Krause, V. Bragoni and L. J. Goossen,
Chem. Eur. J., 2016, 22, 12270.
14(a) X.-Y. Jiang and F.-L. Qing, Angew. Chem., Int. Ed., 2013,
52, 14177; (b) K. Zhang, J.-B. Liu and F.-L. Qing, Chem.
Commun., 2014, 50, 14157; (c) B. Yang, X.-H. Xu and F.-
L. Qing, Org. Lett., 2015, 17, 1906; (d) Q.-Y. Lin, X.-H. Xu,
K. Zhang and F.-L. Qing, Angew. Chem., Int. Ed., 2016,
55, 1479; (e) W. Yu, X.-H. Xu and F.-L. Qing, Org. Lett.,
2016, 18, 5130; (f) B. Yang, X.-H. Xu and F.-L. Qing, Org.
Lett., 2016, 18, 5956.
15For selected examples, see: (a) X. Mi, C. Wang, M. Huang,
J. Zhang, Y. Wu and Y. Wu, Org. Lett., 2014, 16, 3356; (b)
7 (a) P. Nikolaienko, R. Pluta and M. Rueping, Chem. Eur. J.,
2014, 20, 9867; (b) J.-B. Liu, X.-H. Xu, Z.-H. Chen and F.-
L. Qing, Angew. Chem., Int. Ed., 2015, 54, 897; (c) S.
Arimori, M. Takada and N. Shibata, Dalton Trans., 2015,
44, 19456; (d) M. Maeno, N. Shibata and D. Cahard,
Org. Lett., 2015, 17, 1990; (e) X. Dai and D. Cahard,
Synlett, 2015, 26, 40; (f) Q. Glenadel, A. Tlili and T.
Billard, Eur. J. Org. Chem., 2016, 1955.
Y. Li, Y. Lu, G. Qiu and Q. Ding, Org. Lett., 2014, 16
,
4240; (c) W. Wei, J. Wen, D. Yang, M. Guo, Y. Wang, J.
You and H. Wang, Chem. Commun., 2015, 51, 768; (d)
W. Yang, S. Yang, P. Li and L. Wang, Chem. Commun.,
2015, 51, 7520; (e) D. Zheng, J. Yu and J. Wu, Angew.
Chem., Int. Ed., 2016, 55, 11925; (f) S. Ni, J. Cao, H. Mei,
J. Han, S. Li and Y. Pan, Green Chem., 2016, 18, 3935; (g)
S. Feng, X. Xie, W. Zhang, L. Liu, Z. Zhong, D. Xu and X.
She, Org. Lett., 2016, 18, 3846; (h) S. Yang, H. Tan, W. Ji,
X. Zhang, P. Li and L. Wang, Adv. Synth. Catal., 2017,
359, 443.
8 For selected examples, see: (a) G. Teverovskiy, D. S. Surry
and S. L. Buchwald, Angew. Chem., Int. Ed., 2011, 50,
7312; (b) F. Baert, J. Colomb and T. Billard, Angew.
Chem., Int. Ed., 2012, 51, 10382; (c) C.-P. Zhang and D.
A. Vicic, J. Am. Chem. Soc., 2012, 134, 183; (d) M.
Rueping, N. Tolstoluzhsky and P. Nikolaienko, Chem.
Eur. J., 2013, 19, 14043; (e) Y. Huang, X. He, X. Lin, M.
Rong and Z. Weng, Org. Lett., 2014, 16, 3284; (f) G. Yin,
I. Kalvet and F. Schoenebeck, Angew. Chem., Int. Ed.,
2015, 54, 6809; (g) . Zheng, L. Wang, J.-H. Lin, J.-C. Xiao
and S. H. Liang, Angew. Chem., Int. Ed., 2015, 54, 13236;
(h) G. Yin, I. Kalvet, U. Englert and F. Schoenebeck, J.
Am. Chem. Soc., 2015, 137, 4164; (i) M. Zhang and Z.
Weng, Adv. Synth. Catal., 2016, 358, 386.
16(a) S. Ni, Y. Zhang, C. Xie, H. Mei, J. Han and Y. Pan, Org.
Lett., 2015, 17, 5524; (b) T. Miao, D. Xia, Y. Li, P. Li and
L. Wang, Chem. Commun., 2016, 52, 3175; (c) S. Ni, L.
Zhang, W. Zhang, H. Mei, J. Han and Y. Pan, J. Org.
Chem., 2016, 81, 9470; (d) C. Pan, Y. Chen, S. Song, L. Li
and J.-T. Yu, J. Org. Chem., 2016, 81, 12065; (e) D.-L.
Kong, L. Cheng, H.-R. Wu, Y.-X. Li, D. Wang and L. Liu,
Org. Biomol. Chem., 2016, 14, 2210; (f) S. Ni, W. Sha, L.
Zhang, C. Xie, H. Mei, J. Han and Y. Pan, Org. Lett., 2016,
18, 712.
17 F. Yin and X.-S. Wang, Org. Lett., 2014, 16, 1128.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C7CC06232J
The oxidative trifluoromethylthiolation of aryl alkynoates with AgSCF3 provided a
new access to trifluoromethylthiolated alkenes.