Synthesis of vinyl and electron-deficient aryl trifluoromethyl sulfides via Csp2?OH bond activation with AgSCF3 and n-Bu4NI/KI

Article abstract of DOI:10.1016/j.tet.2018.08.036

Direct dehydroxytrifluoromethylthiolation of enols and electron-deficient phenols with AgSCF₃ in the presence of n-Bu₄NI and KI is reported, affording a series of vinyl and aryl trifluoromethyl sulfides in moderate to excellent yields. This work represents a rare example of direct functionalization of Csp²?OH bonds.

Full text of DOI:10.1016/j.tet.2018.08.036

Accepted Manuscript
2
Synthesis of vinyl and electron-deficient aryl trifluoromethyl sulfides via Csp −OH
bond activation with AgSCF and n-Bu NI/KI
3
4
Yin-Li Liu, Xiu-Hua Xu, Feng-Ling Qing
PII:
S0040-4020(18)31002-0
10.1016/j.tet.2018.08.036
TET 29756
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 20 July 2018
Revised Date: 21 August 2018
Accepted Date: 23 August 2018
Please cite this article as: Liu Y-L, Xu X-H, Qing F-L, Synthesis of vinyl and electron-deficient aryl
2
trifluoromethyl sulfides via Csp −OH bond activation with AgSCF and n-Bu NI/KI, Tetrahedron (2018),
3
4
doi: 10.1016/j.tet.2018.08.036.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Synthesis of vinyl and electron-deficient aryl
trifluoromethyl sulfides via Csp2−OH bond
activation with AgSCF3 and n-Bu4NI/KI
Leave this area blank for abstract info.
Yin-Li Liu, Xiu-Hua Xu, Feng-Ling Qing
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic
Chemistry, Chinese Academy of Science, 345 Lingling Lu, Shanghai 200032, China

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Synthesis of vinyl and electron-deficient aryl trifluoromethyl sulfides via Csp2−OH
bond activation with AgSCF3 and n-Bu4NI/KI
Yin-Li Liua, Xiu-Hua Xua, Feng-Ling Qinga,b
aKey Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of
Science, 345 Lingling Lu, Shanghai 200032, China
bKey Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua
University, 2999 North Renmin Lu, Shanghai 201620, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Direct dehydroxytrifluoromethylthiolation of enols and electron-deficient phenols with AgSCF3
in the presence of n-Bu4NI and KI is reported, affording a series of vinyl and aryl
trifluoromethyl sulfides in moderate to excellent yields. This work represents a rare example of
direct functionalization of Csp2−OH bonds.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Trifluoromethylthiolation
Enol
Phenol
C–O activation
Carbonothioic difluoride
1. Introduction
nickel-catalyzed trifluoromethylthiolation of aryl, vinyl triflates
and nonaflates with Me4NSCF3 (Scheme 1b).10b To the best of
our knowledge, the direct trifluoromethylthiolation of Csp2−OH
bonds has never been reported.
The introduction of fluorine atom and fluorine-containing
groups into organic compounds can significantly alter their
chemical, physical, and biological properties.1 For example, the
trifluoromethylthio group (SCF3) has been incorporated into
many pharmaceuticals and agrochemicals such as Fipronil,2a
Tiflorex,2b Toltrazuril,2c and Cefazaflur,2d due to its extremely
high lipophilicity and specific electronic properties.3 Over the
Previous work
OR
SCF3
SCF3
CuCl, phen
(a)
(b)
+ Na2S2O3
+
TMSCF3
K3PO4, DMSO
R = Ms, Ts
OR
past
several
years,
the
development
of
new
trifluoromethylthiolating reagents and trifluoromethylthiolation
reactions have witnessed significant progress.4 Especially,
numerous efforts have been devoted to the synthesis of aryl and
vinyl trifluoromethyl sulfides. A variety of transition-metal-
mediated/catalyzed trifluoromethylthiolation reactions have been
developed for the direct conversion of Csp2−X (X = H,5 B(OR)2,6
CO2H,7 diazonium salt,8 halide9) bonds to Csp2−SCF3 bonds.
However, the direct formation of Csp2−SCF3 bonds from
Csp2−OR bonds remains less explored. To date, only two studies
have been reported, which focused on the coupling of aryl and/or
vinyl sulfonates for the preparation of corresponding
trifluoromethyl sulfides. In 2014, Zhong and Liu exploited a
copper-catalyzed trifluoromethylthiolation of aryl sulfonates
using Na2S2O3 and TMSCF3 as the SCF3 source (Scheme 1a).10a
Ni(cod)2, dppf
toluene
+ Me4NSCF3
R'
R
R'
R = Tf, Nf
This work
OH
SCF3
n-Bu4NI, KI
+
AgSCF3
via
(c)
R
toluene
O
F
R
S
Scheme 1 Direct conversion of Csp2−O bonds to Csp2−SCF3 bonds.
In
2015,
our
group
developed
a
direct
dehydroxytrifluoromethylthiolation of alcohols with AgSCF3 and
Recently, Schoenebeck and co-workers disclosed an efficient
———
Corresponding author. Tel.: +86 21 54925187; fax: +86 21 64166128.
E-mail address: flq@mail.sioc.ac.cn (F.-L. Qing).

2
Tetrahedron
ACCEPTED MANUSCRIPT
n-Bu4NI
on the basis of the equilibrium between
To test our hypothesis, (Z)-ethyl 2-(biphenyl-4-yl)-3-
-
trifluoromethanethiolate (SCF3 ) with carbonothioic difluoride
(S=CF2) and fluoride anion (F-).11a This work not only opened up
new opportunities for direct trifluoromethylthiolation of
Csp3−OH bonds,11 but also stimulated wide interest of the S=CF2
chemistry.12 Encouraged by this work and continuing with our
research on trifluoromethylthiolation reactions,11a,13 herein we
report the first trifluoromethylthiolation of Csp2−OH bonds
(Scheme 1c). This protocol allows a convenient synthesis of
various vinyl and aryl trifluoromethyl sulfides from simple enols
and electron-deficient phenols.
hydroxyacrylate (1a) was chosen as the model substrate for the
dehydroxytrifluoromethylthiolation (Table 1). When 1a was
treated with AgSCF3 (3.0 equiv) and n-Bu4NI (9.0 equiv) in
toluene under the optimal reaction conditions of
dehydroxytrifluoromethylthiolation of alcohols,11a none of the
trifluoromethylthiolated product was observed (entry 1).
Apparently, the dehydroxytrifluoromethylthiolation of Csp2−OH
bonds is more challenging than that of Csp3−OH bonds. To our
delight, the employment of both of n-Bu4NI and KI as the
activator afforded the desired product 2a in 54% yield (entry 2).
Switching the activator from n-Bu4NI to n-Bu4NBr (entry 3) or
from KI to KBr (entry 4) resulted in lower yields. When this
reaction was performed in other solvents including DCE, CH3CN,
and DMF, 2a was formed in lower yields (entries 5-7). The
screening of different temperature revealed that 120 oC was
optimal, delivering 2a in 89% yield (entries 8-10). Notably, a
dramatic drop in the yield was observed when decreasing the
amounts of AgSCF3, n-Bu4NI, and KI (entry 11). Furthermore,
none of the desired product 2a was detected upon using KI as the
activator (entry 12). Finally, other SCF3 sources including
CuSCF3 and Me4NSCF3 were investigated (entries 13-15).
However, both of them were sluggish to this reaction.
2. Results and discussion
Enols and phenols are fundamental structural moieties in
organic chemistry. Consequently, the functionalization of the
enols and phenols has received wide research interest. Normally,
these compounds are first converted to the corresponding
sulfonates or carbonates for further transformations. However,
the direct Csp2−OH bond functionalization were less explored.
Recently, Ritter14 and Sanford15 respectively disclosed
deoxyfluorination of phenols with PhenoFluor or SO2F2/NMe4F.
Inspired by these work, we hypothesized that direct
trifluoromethylthiolation of Csp2−OH bonds should be feasible
by adopting our dehydroxytrifluoromethylthiolation strategy.11a
We envisioned that the activation of AgSCF3 with n-Bu4NI
would result in the formation of active source of [SCF3]-,16 which
decomposed to generate carbonothioic difluoride (S=CF2). Then,
the reaction of Csp2−OH with S=CF2 formed Csp2−OC(S)F
intermediates, which could be substituted by [SCF3]- to afford the
final product (Scheme 1c).
Table 1. Optimization of reaction conditions.a
Entry Activator
Solvent
Temperature Yield (%)b
1
n-Bu4NI
toluene
toluene
toluene
toluene
DCE
80 oC
0
2
n-Bu4NI + KI
n-Bu4NBr + KI
n-Bu4NI + KBr
n-Bu4NI + KI
n-Bu4NI + KI
n-Bu4NI + KI
n-Bu4NI + KI
n-Bu4NI + KI
n-Bu4NI + KI
n-Bu4NI + KI
KI
80 oC
54
17
8
3
80 oC
4
80 oC
5
80 oC
12
30
trace
68
89
72
43
0
6
CH3CN
DMF
80 oC
7
80 oC
8
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
100 oC
120 oC
140 oC
120 oC
120 oC
120 oC
120 oC
120 oC
9
10
11c
12
13d
14e
15e
n-Bu4NI + KI
—
0
0
KI
trace
aReaction conditions: 1a (0.2 mmol), AgSCF3 (0.6 mmol), n-Bu4NI (1.8
mmol), KI (1.2 mmol), solvent (2.0 mL), under N2, temperature, 5 h.
bYields determined by 19F NMR spectroscopy using trifluoromethylbenzene
as an internal standard.
Scheme 2 Substrate scope of dehydroxytrifluoromethylthiolation of
enols. Reaction conditions: 1 (0.2 mmol), AgSCF3 (0.6 mmol), n-
Bu4NI (1.8 mmol), KI (1.2 mmol), toluene (2.0 mL), under N2, 120
oC, 5 h. Yields are those of isolated products. E/Z ratios were
determined by 19F NMR spectroscopy of the crude reaction mixture.
a
cAgSCF3 (0.4 mmol), n-Bu4NI (1.2 mmol), KI (0.8 mmol).
dCuSCF3 (0.6 mmol).
eMe4NSCF3 (0.6 mmol).
With the optimized conditions (Table 1, entry 9) in hand, we
then
investigated
the
substrate
scope
of

3
dehydroxytrifluoromethylthiolation of enols. As shown in
Scheme 2, a series of enols 1a-k underwent this transformation
smoothly, furnishing the trifluoromethylthiolated alkenes 2a-k in
high yields and excellent E/Z selectivities. The configuration of
product 2 was determined by comparison of the 19F NMR
spectroscopy with that of the literature data,17 suggesting an E
configuration of the major isomer. This reaction system was
compatible with electronically diverse functionalities, including
alkyl (1c,d), alkoxy (1k), aryl (1a), cyano (1e), nitro (1f,k),
fluoro (1g), bromo (1h-j), trifluoromethyl (1i), and
trifluoromethoxy (1j) substituents. Additionally, naphthyl-
substituted enols 1l-n were also applicable substrates, the
transformation of which provided the corresponding products in
moderate to high yields. In the case of substrate (1o) containing
benzofuran heterocycle, the desired product was obtained in 61%
yield and excellent E/Z selectivity.
of the reaction conditions, including changing the solvent,
ACCEPTED MANUSCRIPT
increasing the amounts of reagents, and elevating the reaction
temperature, the dehydroxytrifluoromethylthiolation of electron-
deficient phenols 5a and 5b proceeded well, affording the
corresponding trifluoromethyl sulfides 6a and 6b in moderate
yields, respectively (Scheme 4). It was as noteworthy that
electron-rich and -neutral phenols were not suitable substrates for
this reaction.
In conclusion, we have developed an efficient method for the
transforming of enols and electron-deficient phenols to the
corresponding vinyl and aryl trifluoromethyl sulfides. The
activation of AgSCF3 with n-Bu4NI and KI in toluene is the key
to this Csp2−OH bond transformation. A wide panel of functional
groups was well tolerated under the reaction conditions, and the
desired products were obtained in moderate to excellent yields.
Further
investigations
of
other
This dehydroxytrifluoromethylthiolation protocol could also
be extended to other types of enols. For example, enols 3a-e
derived from oxindoles were successfully converted to the
trifluoromethylthiolated products in high yields, albeit with low
Z/E selectivities (Scheme 3). Considering the biological
importance of oxindole scaffolds,18 the resulting SCF3-containing
oxindole derivatives might be potentially useful in drug
discovery.
dehydroxytrifluoromethylthiolation reactions are currently in
progress in our laboratory.
3. Experimental section
3.1. General information
1H and 19F NMR (CFCl3 as outside standard and low field is
positive) spectra were recorded on
a Bruker AM 400
spectrometer. 13C NMR spectra were recorded on a Bruker AM
400 spectrometer. Chemical shifts (δ) were reported in ppm, and
coupling consta nts (J) were in Hertz (Hz). The following
abbreviations were used to explain the multiplicities: s = singlet,
d = doublet, t = triplet, q = quartet, m = multiplet, br = broad.
High resolution mass spectra (HRMS) were performed using a
GC/MS TOF high-resolution mass spectrometer equipped with a
liquid chromatography system. Unless otherwise noted, all
reagents were obtained commercially and used without further
purification. The synthesis of enols 1a-o and 3a-e were reported
in detail in supporting information.
3.2. General procedure for dehydroxytrifluoromethylthiolation of
enols
A 25 mL Schlenk tube equipped with a magnetic stirring bar
was charged with AgSCF3 (125.3 mg, 0.6 mmol), n-Bu4NI (664.9
mg, 1.8 mmol), and KI (199.2 mg, 1.2 mmol). The tube was
evacuated and backfilled with N2 for three times. Then, enol (0.2
mmol) and toluene (2.0 mL) were added to the tube. The tube
was placed into a preheated oil bath at 120 °C with vigorous
stirring. After 5 h, the reaction mixture was cooled to room
temperature and filtered through a plug of silica (eluted with
EtOAc). The filtrate was concentrated, and the product was
purified by column chromatography on silica gel to give the
desired product.
Scheme 3 Substrate scope of dehydroxytrifluoromethylthiolation of
enols derived from oxindoles. Reaction conditions: 3 (0.2 mmol),
AgSCF3 (0.6 mmol), n-Bu4NI (1.8 mmol), KI (1.2 mmol), toluene
(2.0 mL), under N2, 120 oC, 5 h. Yields are those of isolated products.
E/Z ratios were determined by 19F NMR spectroscopy of the crude
reaction mixture.
a
3.2.1. (E)-Ethyl 2-(biphenyl-4-yl)-3-
(trifluoromethylthio)acrylate (2a)
Yield 85% (58.8 mg), red oil, eluent for column
chromatography: hexane/EtOAc (20:1).
1H NMR (400 MHz,
CDCl3): δ 7.80 (s, 1H), 7.61 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 7.6
Hz, 2H), 7.36 (d, J = 7.3 Hz, 2H), 7.31-7.04 (m, 3H), 4.28 (q, J =
7.1 Hz, 2H), 1.31 (t, J = 7.1 Hz, 3H); 19F NMR (376 MHz,
CDCl3): δ -42.04 (s, 3F); 13C NMR (101 MHz, CDCl3): δ 164.1,
141.7, 140.4, 133.2, 132.4, 131.1 (q, J = 3.5 Hz), 129.3, 128.9 (q,
J = 310.3 Hz), 127.6, 127.2, 127.1, 61.6, 14.2; IR (thin film) ν
2984, 1717, 1488, 1369, 1237, 1111, 1036, 908 cm-1; MS (ESI):
m/z 353 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C18H16F3O2S [M+H]+: 353.0815; Found: 353.0818.
Scheme 4 Dehydroxytrifluoromethylthiolation of electron-deficient
phenols.
To further enlighten the synthetic utility of this method, we
then
turned
our
attention
to
the
dehydroxytrifluoromethylthiolation of phenols. However, low
yield was obtained when phenol 5a was subjected to the standard
reaction conditions (Table 1, entry 9). After slightly modification
3.2.2. (E)-Ethyl 2-phenyl-3-
(trifluoromethylthio)acrylate (2b)

4
Tetrahedron
ACCEPTED MANUSCRIPT
Yield 61% (33.7 mg), red oil, eluent for column
CDCl3): δ 7.79 (s, 1H), 7.30-7.25 (m, 2H), 7.17-7.13 (m, 2H),
chromatography: hexane/EtOAc (60:1)
.
1H NMR (400 MHz,
4.30 (q, J = 7.1 Hz, 2H), 1.35 (t, J = 7.1 Hz, 3H); 19F NMR (376
CDCl3): δ 7.79 (s, 1H), 7.45-7.35 (m, 3H), 7.25 (d, J = 8.0 Hz,
2H), 4.27 (q, J = 7.1 Hz, 2H), 1.30 (t, J = 7.1 Hz, 3H); 19F NMR
(376 MHz, CDCl3): δ -42.09 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 164.1, 133.6, 133.5, 131.1 (q, J = 3.5 Hz), 130.4, 128.9
(q, J = 310.1 Hz), 128.5, 124.9, 61.6, 14.2; IR (thin film) ν 2984,
1713, 1494, 1369, 1238, 1112, 1041, 907 cm-1; MS (ESI): m/z
277 [M+H]+; HRMS (ESI-TOF): m/z Calculated for C12H12F3O2S
[M+H]+: 277.0505; Found: 277.0503.
MHz, CDCl3): δ -41.96 (s, 3F), -111.87 to -111.95 (m, 1F); 13C
NMR (101 MHz, CDCl3): δ 163.9, 162.8 (d, J = 249.5 Hz),
132.6, 131.6 (q, J = 3.0 Hz), 130.9, 130.8, 129.4, 128.8 (q, J =
310.1 Hz), 115.8, 115.6, 61.7, 14.2; IR (thin film) ν 2985, 1714,
1509, 1369, 1236, 1112, 1036, 907 cm-1; MS (ESI): m/z 295
[M+H]+; HRMS (ESI-TOF): m/z Calculated for C12H11F4O2S
[M+H]+: 295.0410; Found: 295.0408.
3.2.8. (E)-Ethyl 2-(2,5-dibromophenyl)-3-
(trifluoromethylthio)acrylate (2h)
3.2.3. (E)-Ethyl 2-p-tolyl-3-
(trifluoromethylthio)acrylate (2c)
Yield 53% (46.0 mg), red oil, eluent for column
Yield 50% (29.2 mg), red oil, eluent for column
chromatography: hexane/EtOAc (15:1).
1H NMR (400 MHz,
chromatography: hexane/EtOAc (20:1)
.
1H NMR (400 MHz,
CDCl3): δ 7.87 (s, 1H), 7.49 (d, J = 8.5 Hz, 1H), 7.37 (dd, J =
8.5, 2.4 Hz, 1H), 7.30 (d, J = 2.3 Hz, 1H), 4.23 (q, J = 7.1 Hz,
2H), 1.26 (t, J = 7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3): δ -
41.32 (s, 3F); 13C NMR (101 MHz, CDCl3): δ 162.7, 136.4,
134.5, 131.6 (q, J = 4.0 Hz), 133.6, 133.3, 132.2, 128.6 (q, J =
310.1 Hz), 122.2, 121.3, 61.9, 14.1; IR (thin film) ν 2983, 1715,
1455, 1384, 1283, 1108, 1050, 907 cm-1; MS (ESI): m/z 433
[M+H]+; HRMS (ESI-TOF): m/z Calculated for C12H10Br2F3O2S
[M+H]+: 432.8715; Found: 432.8713.
CDCl3): δ 7.76 (s, 1H), 7.18 (d, J = 7.7 Hz, 2H), 7.12 (d, J = 6.7
Hz, 2H), 4.29-4.23 (m, 2H), 2.37 (s, 3H), 1.44-1.39 (m, 3H); 19F
NMR (376 MHz, CDCl3): δ -42.16 (s, 2.6F), -45.48 (s, 0.4F); 13
C
NMR (101 MHz, CDCl3): δ 164.3, 138.9, 130.7 (q, J = 4.0 Hz),
130.5, 129.3, 128.8, 128.6 (q, J = 295.3 Hz), 124.4, 61.6, 21.4,
14.2; IR (thin film) ν 2985, 1716, 1511, 1369, 1237, 1112, 1039,
908 cm-1; MS (ESI): m/z 291 [M+H]+; HRMS (ESI-TOF): m/z
Calculated for C13H14F3O2S [M+H]+: 291.0661; Found:
291.0659.
3.2.9. (E)-Ethyl 2-(2-bromo-5-
(trifluoromethyl)phenyl)-3-
(trifluoromethylthio)acrylate (2i)
3.2.4. (E)-Ethyl 2-(4-tert-butylphenyl)-3-
(trifluoromethylthio)acrylate (2d)
Yield 46% (38.8 mg), red oil, eluent for column
Yield 78% (51.8 mg), red oil, eluent for column
.
1H NMR (400 MHz,
chromatography: hexane/EtOAc (20:1).
1H NMR (400 MHz,
chromatography: hexane/EtOAc (20:1)
CDCl3): δ 7.92 (s, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.53-7.47 (m,
1H), 7.43 (s, 1H), 4.33-4.25 (m, 2H), 1.26 (t, J = 7.1 Hz, 3H); 19
CDCl3): δ 7.76 (s, 1H), 7.43 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.0
Hz, 2H), 4.28 (q, J = 7.2 Hz, 2H), 1.34-1.31 (m, 12H); 19F NMR
(376 MHz, CDCl3): δ -42.19 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 164.3, 151.9, 133.5, 130.6 (q, J = 3.1 Hz), 130.4, 129.0
(q, J = 311.1 Hz), 128.6, 125.5, 61.6, 34.7, 31.2, 14.2; IR (thin
film) ν 2966, 1717, 1508, 1368, 1237, 1112, 1040, 908 cm-1; MS
(ESI): m/z 333 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C13H14F3O2S [M+H]+: 333.1131; Found: 333.1129.
F
NMR (376 MHz, CDCl3): δ -41.31 (s, 3F), -62.75 (s, 3F); 13C
NMR (101 MHz, CDCl3): δ 162.6, 135.5, 133.9 (q, J = 3.6 Hz),
133.8, 132.3, 130.4 (q, J = 33.3 Hz), 128.8 (q, J = 310.0 Hz),
127.6, 127.5 (q, J = 3.7 Hz), 127.2 (q, J = 3.6 Hz), 125.9 (q, J =
225.6 Hz), 62.0, 14.1; IR (thin film) ν 2888, 1696, 1571, 1429,
1203, 1070, 906, 777 cm-1; MS (ESI): m/z 423 [M+H]+; HRMS
(ESI-TOF): m/z Calculated for C13H10BrF6O2S [M+H]+:
422.9484; Found: 422.9482.
3.2.5. (E)-Ethyl 2-(4-cyanophenyl)-3-
(trifluoromethylthio)acrylate (2e)
3.2.10. (E)-Ethyl 2-(3-bromo-4-
(trifluoromethoxy)phenyl)-3-
(trifluoromethylthio)acrylate (2j)
Yield 86% (51.8 mg), red oil, eluent for column
chromatography: hexane/CH2Cl2 (1:1).
1H NMR (400 MHz,
CDCl3): δ 7.86 (s, 1H), 7.69 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.0
Hz, 2H), 4.25 (q, J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H); 19F
NMR (376 MHz, CDCl3): δ -41.75 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 163.2, 138.1, 132.8 (q, J = 4.0 Hz), 132.3, 131.9,
129.9, 128.5 (q, J = 310.1 Hz), 118.3, 112.8, 62.0, 14.1; IR (thin
film) ν 2985, 2232, 1714, 1369, 1240, 1108, 1037, 909 cm-1; MS
(ESI): m/z 302 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C13H11F3NO2S [M+H]+: 302.0457; Found: 302.0454.
Yield 91% (80.2 mg), red oil, eluent for column
chromatography: hexane/EtOAc (10:1).
1H NMR (400 MHz,
CDCl3): δ 7.85 (s, 1H), 7.54 (d, J = 2.1 Hz, 1H), 7.34 (dd, J =
8.5, 1.4 Hz, 1H), 7.25-7.20 (m, 1H), 4.26 (q, J = 7.1 Hz, 2H),
1.30 (t, J = 7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3): δ -41.86
(s, 2.93F), -45.38 (s, 0.07F), -57.54 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 163.3, 146.7, 134.7, 132.8 (q, J = 4.0 Hz), 131.1,
129.5, 128.6 (q, J = 310.1 Hz), 121.9, 120.8 (q, J = 260.1 Hz),
116.2, 61.9, 14.1; MS (ESI): m/z 439 [M+H]+; HRMS (ESI-
TOF): m/z Calculated for C13H10BrF6O3S [M+H]+: 438.9433;
Found: 438.9435.
3.2.6. (E)-Ethyl 2-(4-nitrophenyl)-3-
(trifluoromethylthio)acrylate (2f)
Yield 57% (36.6 mg), red oil, eluent for column
chromatography: hexane/EtOAc (20:1).
1H NMR (400 MHz,
3.2.11. (E)-Ethyl 2-(4-methoxy-3-nitrophenyl)-3-
(trifluoromethylthio)acrylate (2k)
CDCl3): δ 8.29 (d, J = 8.8 Hz, 2H), 7.93 (s, 1H), 7.46 (d, J = 8.8
Hz, 2H), 4.30 (q, J = 7.2 Hz, 2H), 1.32 (t, J = 7.2 Hz, 3H); 19F
NMR (376 MHz, CDCl3): δ -41.70 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 163.1, 147.9, 140.0, 133.1 (q, J = 4.0 Hz), 130.2, 128.5
(q, J = 311.1 Hz), 124.9, 123.8, 62.1, 14.2; IR (thin film) ν 2985,
1716, 1511, 1369, 1237, 1112, 1039, 908 cm-1; MS (ESI): m/z
322 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C12H11F3NO4S [M+H]+: 322.0355; Found: 322.0354.
Yield 41% (28.8 mg), red oil, eluent for column
chromatography: hexane/EtOAc (6:1)
.
1H NMR (400 MHz,
CDCl3): δ 7.83 (d, J = 9.6 Hz, 1H), 7.77 (d, J = 2.1 Hz, 1H), 7.43
(dd, J = 8.7, 2.2 Hz, 1H), 7.11 (d, J = 7.8 Hz, 1H), 4.29 (q, J =
7.2 Hz, 2H), 3.97 (s, 3H), 1.33 (t, J = 7.2 Hz, 3H); 19F NMR (376
MHz, CDCl3): δ -41.73 (s, 2.86F), -45.29 (s, 0.14F); 13C NMR
(101 MHz, CDCl3): δ 163.5, 153.2, 139.4, 134.9, 132.5 (q, J =
3.0 Hz), 130.9, 128.6 (q, J = 310.1 Hz), 126.7, 125.6, 113.6, 62.0,
56.7, 14.2; IR (thin film) ν 2986, 1716, 1533, 1352, 1240, 1110,
1017, 804 cm-1; MS (ESI): m/z 352 [M+H]+; HRMS (ESI-TOF):
3.2.7. (E)-Ethyl 2-(4-fluorophenyl)-3-
(trifluoromethylthio)acrylate (2g)
Yield 63% (37.0 mg), red oil, eluent for column
chromatography: hexane/EtOAc (30:1).
1H NMR (400 MHz,

5
m/z Calculated for C13H13F3NO5S [M+H]+: 352.0641; Found:
352.0640.
41.83 (s, 1.2F), -44.30 (s, 1.8F); 13C NMR (101 MHz, CDCl3):
ACCEPTED MANUSCRIPT
δ 166.6, 165.2, 142.9, 141.7, 135.6, 135.5, 130.1, 129.4, 129.0 (q,
J = 311.1Hz), 128.8, 128.5 (q, J = 311.1 Hz), 127.8, 127.7, 127.4,
127.2, 125.1 (q, J = 4.0 Hz), 125.0, 124.6 (q, J = 4.0 Hz), 124.1,
122.5, 122.4, 119.9, 109.5, 109.4, 43.8, 43.7; IR (thin film) ν
2925, 1694, 1610, 1496, 1335, 1115, 906, 771 cm-1; MS (ESI):
m/z 336 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C17H13F3NOS [M+H]+: 336.0664; Found: 336.0663.
3.2.12. (E)-Ethyl 2-(naphthalen-2-yl)-3-
(trifluoromethylthio)acrylate (2l)
Yield 81% (52.8 mg), red oil, eluent for column
chromatography: hexane/EtOAc (50:1).
1H NMR (400 MHz,
CDCl3): δ 7.91-7.85 (m, 4H), 7.72 (s, 1H), 7.52 (t, J = 3.6 Hz,
2H), 7.36 (d, J = 8.8, 1H), 4.31 (q, J = 7.2 Hz, 2H), 1.31 (t, J =
7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3): δ -42.04 (s, 3F); 13C
NMR (101 MHz, CDCl3): δ 164.1, 133.2, 132.9, 131.6 (q, J = 4.0
Hz), 131.1, 128.9 (q, J = 310.1 Hz), 128.5, 128.3, 128.2, 127.8,
126.9, 126.5, 126.3, 61.7, 14.2; IR (thin film) ν 2983, 1715,
1369, 1235, 1110, 1040, 906 cm-1; MS (ESI): m/z 327 [M+H]+;
HRMS (ESI-TOF): m/z Calculated for C16H14F3O2S [M+H]+:
327.0661; Found: 327.0658.
3.2.17. 1-Methyl-3-
((trifluoromethylthio)methylene)indolin-2-one (4b)
Yield 70% (36.3 mg), brown solid, eluent for column
chromatography: hexane/EtOAc (10:1).
1H NMR (400 MHz,
CDCl3): δ 7.73 (s, 0.25H), 7.51 (s, 0.75H), 7.46-7.31 (m, 2H),
7.12-7.07 (m, 1H), 6.88-6.84 (m, 1H), 3.28 (s, 2.25H), 3.26 (s,
0.75H); 19F NMR (376 MHz, CDCl3): δ -41.86 (s, 0.75F), -44.35
(s, 2.25F); 13C NMR (101 MHz, CDCl3): δ 166.6, 142.6, 130.1,
129.5 (q, J = 311.1 Hz), 129.4, 124.7 (q, J = 4.0 Hz), 124.0,
122.4, 122.3, 120.8, 119.9, 108.5, 108.3, 29.7, 25.9; IR (thin
film) ν 2925, 1682, 1609, 1469, 1379, 1281, 1117, 906 cm-1; MS
(ESI): m/z 260 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C11H9F3NOS [M+H]+: 260.0351; Found: 260.0351.
3.2.13. (E)-Ethyl 2-(1-bromonaphthalen-2-yl)-3-
(trifluoromethylthio)acrylate (2m)
Yield 74% (60.0 mg), red oil, eluent for column
chromatography: hexane/EtOAc (20:1).
1H NMR (400 MHz,
CDCl3): δ 8.37 (d, J = 8.4 Hz, 1H), 8.00 (s, 1H), 7.90 (d, J = 8.4
Hz, 2H), 7.69-7.62 (m, 2H), 7.29 (s, 1H), 4.25 (q, J = 7.1 Hz,
2H), 1.21 (t, J = 7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3): δ -
41.39 (s, 3F); 13C NMR (101 MHz, CDCl3): δ 163.3, 134.3,
132.6, 132.3, 131.6 (q, J = 5.0 Hz), 128.9 (q, J = 310.1 Hz),
128.5, 128.3, 127.8, 127.6, 127.4, 126.6, 124.1, 61.7, 14.2; IR
(thin film) ν 2984, 1716, 1587, 1371, 1238, 1111, 905, 732 cm-1;
MS (ESI): m/z 405 [M+H]+; HRMS (ESI-TOF): m/z Calculated
for C16H13BrF3O2S [M+H]+: 404.9766; Found: 404.9763.
3.2.18. 1-Phenyl-3-
((trifluoromethylthio)methylene)indolin-2-one (4c)
Yield 73% (46.9 mg), brown solid, eluent for column
chromatography: hexane/EtOAc (8:1)
.
1H NMR (400 MHz,
CDCl3): δ 7.84 (s, 0.33H), 7.64 (s, 0.67H), 7.56-7.41 (m, 6H),
7.29 (s, 0.33H), 7.25 (s, 0.67H), 7.16-7.12 (m, 1H), 6.92 (d, J =
6.92 Hz, 0.67 H), 6.86 (d, J = 6.86 Hz, 0.33 H); 19F NMR (376
MHz, CDCl3): δ -41.78 (s, 1F), -44.37 (s, 2F); 13C NMR (101
MHz, CDCl3): δ 166.0, 164.5, 143.7, 142.5 133.9, 130.1, 129.7,
129.6, 129.5 (q, J = 311.1 Hz), 129.4, 128.5 (q, J = 311.1 Hz),
128.2, 128.2, 126.6, 126.2, 125.7 (q, J = 4.0 Hz), 124.9 (q, J =
4.0 Hz), 124.3, 123.0, 122.9, 121.0, 120.1, 110.0, 109.7; MS
(ESI): m/z 322 [M+H]+; HRMS (ESI-TOF): m/z Calculated for
C16H11F3NOS [M+H]+: 322.0508; Found: 322.0506.
3.2.14. (E)-Ethyl 2-(6-methoxynaphthalen-2-yl)-3-
(trifluoromethylthio)acrylate (2n)
Yield 66% (47.1 mg), red oil, eluent for column
chromatography: hexane/EtOAc (30:1).
1H NMR (400 MHz,
CDCl3): δ 7.86 (s, 1H), 7.78-7.72 (m, 2H), 7.64 (s, 1H), 7.32 (d, J
= 10.0 Hz, 1H), 7.19-7.15 (m, 2H), 4.29 (q, J = 7.1 Hz, 2H), 3.92
(s, 3H), 1.26 (t, J = 7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3): δ -
42.09 (s, 3F); 13C NMR (101 MHz, CDCl3): δ 164.3, 158.5,
134.6, 133.7, 131.2 (q, J = 3.0 Hz), 129.7, 129.0 (q, J = 311.1
Hz), 128.8, 128.4, 128.3, 127.2, 126.9, 119.5, 105.8, 61.6, 55.4,
14.2; MS (ESI): m/z 357 [M+H]+; HRMS (ESI-TOF): m/z
Calculated for C17H16F3O3S [M+H]+: 357.0767; Found:
357.0764.
3.2.19. 1-Benzyl-5-methoxy-3-
((trifluoromethylthio)methylene)indolin-2-one (4d)
Yield 74% (54.0 mg), brown solid, eluent for column
chromatography: hexane/EtOAc (9:1)
.
1H NMR (400 MHz,
CDCl3): δ 7.81 (s, 0.5H), 7.54 (s, 0.5H), 7.32-7.28 (m, 5H), 7.03
(d, J = 2.4 Hz, 0.5H), 7.02 (d, J = 2.4 Hz, 0.5H), 6.77-6.74 (m,
1H), 6.66-6.61 (m, 1H), 4.94 (s, 2H), 3.80 (s, 3H); 19F NMR (376
MHz, CDCl3): δ -41.78 (s, 1.5F), -44.30 (s, 1.5F); 13C NMR (101
MHz, CDCl3): δ 166.6, 165.1, 155.9, 155.7, 136.6, 135.7, 135.6,
129.5 (q, J = 311.1 Hz), 128.8, 128.5 (q, J = 310.1 Hz), 127.8,
127.7, 127.5, 127.4, 127.3, 125.2 (q, J = 4.0 Hz), 124.8 (q, J =
4.0 Hz), 121.8, 121.6, 114.9, 114.5, 111.4, 110.2, 109.8, 106.3,
55.9, 43.9, 43.8; IR (thin film) ν 2934, 1691, 1593, 1484, 1364,
1287, 1104, 1021 cm-1; MS (ESI): m/z 366 [M+H]+; HRMS (ESI-
TOF): m/z Calculated for C18H15F3NO2S [M+H]+: 366.0770;
Found: 366.0770.
3.2.15. (E)-Ethyl 2-(benzofuran-5-yl)-3-
(trifluoromethylthio)acrylate (2o)
Yield 61% (38.6 mg), red oil, eluent for column
chromatography: hexane/EtOAc (15:1).
1H NMR (400 MHz,
CDCl3): δ 7.80 (s, 1H), 7.65 (d, J = 2.1 Hz, 1H), 7.53 (d, J = 8.6
Hz, 1H), 7.46 (s, 1H), 7.15 (d, J = 6.9 Hz, 1H), 6.77 (d, J = 1.2
Hz, 1H), 4.26 (q, J = 7.1 Hz, 2H), 1.29 (t, J = 7.1 Hz, 3H); 19F
NMR (376 MHz, CDCl3): δ -42.05 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 164.3, 154.9, 145.8, 133.8, 131.4 (q, J = 3.0 Hz), 128.9
(q, J = 310.1 Hz), 128.2, 127.7, 125.2, 122.0, 111.7, 106.8, 61.7,
14.3; IR (thin film) ν 2984, 1715, 1468, 1368, 1236, 1109, 1032,
908 cm-1; MS (ESI): m/z 317 [M+H]+; HRMS (ESI-TOF): m/z
Calculated for C14H12F3O3S [M+H]+: 317.0454; Found:
317.0452.
3.2.20. 1-Benzyl-5-bromo-3-
((trifluoromethylthio)methylene)indolin-2-one (4e)
Yield 70% (57.6 mg), brown solid, eluent for column
chromatography: hexane/EtOAc (3:1)
.
1H NMR (400 MHz,
CDCl3): δ 7.88 (s, 0.45H), 7.62 (s, 0.55H), 7.59 (d, J = 2.1 Hz,
0.55H), 7.51 (d, J = 2.1 Hz, 0.45H), 7.35-7.28 (m, 6H), 6.64 (d, J
= 8.4 Hz, 0.55H), 6.62 (d, J = 8.4 Hz, 0.45H), 4.96 (s, 1.1H),
4.95 (s, 0.9H); 19F NMR (376 MHz, CDCl3): δ -41.62 (s, 1.35F),
-44.19 (s, 1.65F); 13C NMR (101 MHz, CDCl3): δ 164.8, 141.7,
135.1, 133.5 (q, J = 311.1 Hz), 132.6, 129.5 (q, J = 310.1 Hz),
128.9, 128.0, 127.9 (q, J = 4.4 Hz), 127.7, 127.3, 127.2, 126.9,
126.6 (q, J = 4.0 Hz), 125.0, 123.0, 122.4, 115.1, 111.0, 110.8,
3.2.16. 1-Benzyl-3-
((trifluoromethylthio)methylene)indolin-2-one (4a)
Yield 78% (53.2 mg), brown solid, eluent for column
chromatography: hexane/EtOAc (6:1)
CDCl3): δ 7.81 (s, 0.40H), 7.57 (s, 0.60H), 7.46 (d, J = 7.6 Hz,
0.60H), 7.41 (d, J = 7.6 Hz, 0.40H), 7.35-7.20 (m, 6H), 7.09-7.04
(m, 1H), 6.78 (d, J = 8.0 Hz, 0.60H), 6.75 (d, J = 8.0 Hz, 0.40H),
4.97 (s, 1.20H), 4.96 (s, 0.80H); 19F NMR (376 MHz, CDCl3): δ -
.
1H NMR (400 MHz,

6
Tetrahedron
ACCEPTED MANUSCRIPT
Angew. Chem., Int. Ed. 2013, 52, 8214. (c) Chu, L.; Qing, F.-L.
43.9, 43.8; IR (thin film) ν 2936, 1706, 1604, 1471, 1338, 1106,
908, 730 cm-1; MS (ESI): m/z 414 [M+H]+; HRMS (ESI-TOF):
m/z Calculated for C17H12BrF3NOS [M+H]+: 413.9770; Found:
413.9768.
Acc. Chem. Res. 2014, 47, 1513. (d) Toulgoat, F.; Alazet, S.;
Billard, T. Eur. J. Org. Chem. 2014, 2415. (e) Shao, X.; Xu, C.;
Lu, L.; Shen, Q. Acc. Chem. Res. 2015, 48, 1227. (f) Zhang, K.;
Xu, X.-H.; Qing, F.-L. Chin. J. Org. Chem. 2015, 35, 556. (g) Xu,
X.-H.; Matsuzaki, K.; Shibata, N. Chem. Rev. 2015, 115, 731. (h)
Yang, X.; Wu, T.; Phipps, R. J.; Toste, F. D. Chem. Rev. 2015,
115, 826. (i) Chachignon, H.; Cahard, D. Chin. J. Chem. 2016, 34,
445. (j) Barata-Vallejo, S.; Bonesi, S.; Postigo, A. Org. Biomol.
Chem. 2016, 14, 7150. (k) Zheng, H.; Huang, Y.; Weng, Z.
Tetrahedron Lett. 2016, 57, 1397.
3.3. General procedure for dehydroxytrifluoromethylthiolation of
phenols
A 25 mL Schlenk tube equipped with a magnetic stirring bar
was charged with AgSCF3 (417.9 mg, 2.0 mmol), n-Bu4NI (2.22
g, 6.0 mmol), and KI (664.0 mg, 4.0 mmol). The tube was
evacuated and backfilled with N2 for three times. Then, phenol
(0.5 mmol) and xylene (5.0 mL) were added to the tube. The tube
was placed into a preheated oil bath at 150 °C with vigorous
stirring. After 5 h, the reaction mixture was cooled to room
temperature and filtered through a plug of silica (eluted with
EtOAc). The filtrate was concentrated, and the product was
purified by column chromatography on silica gel to give the
desired product.
5. For selected examples, see: (a) Tran, L. D.; Popow, I.; Daugulis,
O. J. Am. Chem. Soc. 2012, 134, 18237. (b) Yang, Y.-D.; Azuma,
A.; Tokunaga, E.; Yamasaki, M.; Shiro, M.; Shibata, N. J. Am.
Chem. Soc. 2015, 135, 8782. (c) Xu, C.; Shen, Q. Org. Lett. 2014,
16, 2046. (d) Jiang, L.; Qian, J.; Yi, W.; Lu, G.; Cai, C.; Zhang,
W. Angew. Chem., Int. Ed. 2015, 54, 14965. (e) Zhang, P.; Li, M.;
Xue, X.-S.; Xu, C.; Zhao, Q.; Liu, Y.; Wang, H.; Guo, Y.; Lv, L.;
Shen, Q. J. Org. Chem. 2016, 81, 7486. (f) Chachignon, H.;
Maeno, M.; Kondo, H.; Shibata, N.; Cahard, D. Org. Lett. 2016,
18, 2467. (g) Milandou, L. J. C. B.; Carreyre, H.; Alazet, S.;
Greco, G.; Martin-Mingot, A.; Loumpangou, C. N.; Ouamba, J.-
M.; Bouazza, F.; Billard, T.; Thibaudeau, S. Angew. Chem., Int.
Ed. 2017, 56, 169. (h) Yoshida, M.; Kawai, K.; Tanaka, R.;
Yoshino, T.; Matsunaga, S. Chem. Commun. 2017, 53, 5974. (i)
Nalbandian, C. J.; Brown, Z. E.; Alvarez, E.; Gustafson, J. L. Org.
Lett. 2018, 20, 3211.
3.3.1. 4-(Trifluoromethylthio)benzonitrile (6a)
Yield 47% (47.8 mg), white solid, eluent for column
chromatography: hexane/EtOAc (10:1).
1H NMR (400 MHz,
CDCl3): δ 7.76 (d, J = 8.0 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H); 19F
NMR (376 MHz, CDCl3): δ -41.95 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 136.0, 132.9, 132.6 (q, J = 3.0 Hz), 129.0 (q, J = 310.1
Hz), 117.6, 114.6; MS (ESI): m/z 204 [M+H]+; HRMS (ESI-
TOF): m/z Calculated for C8H5F3NS [M+H]+: 204.0089; Found:
204.0091.
6. For selected examples, see: (a) Chen, C.; Xie, Y.; Chu, L.; Wang,
R.-W.; Zhang, X.; Qing, F.-L. Angew. Chem., Int. Ed. 2012, 51,
2492. (b) Zhang, C.-P.; Vicic, D. A. Chem. Asian J. 2012, 7, 1756.
(c) Shao, X.; Wang, X.; Yang, T.; Lu, L.; Shen, Q. Angew. Chem.,
Int. Ed. 2013, 52, 3457. (d) Pluta, R.; Nikolaienko, P.; Rueping,
M. Angew. Chem., Int. Ed. 2014, 53, 1650. (e) Glenadel, Q.;
Alazet, S.; Tlili, A.; Billard, T. Chem. Eur. J. 2015, 21, 14694. (f)
Wu, W.; Wang, B.; Ji, X.; Cao, S. Org. Chem. Front. 2017, 4,
1299.
3.3.2. Ethyl 3-nitro-4-(trifluoromethylthio)benzoate
(6b)
7. (a) Pan, S.; Huang, Y.; Qing, F.-L. Chem. Asian J. 2016, 11, 2854.
(b) Li, M.; Petersen, J. L.; Hoover, J. M. Org. Lett. 2017, 19, 638.
(c) Cheng, Z.-F.; Tao, T.-T.; Feng, Y.-S.; Tang, W.-K.; Xu, J.;
Dai, J.-J.; Xu, H.-J. J. Org. Chem. 2018, 83, 499.
Yield 62% (91.5 mg), white solid, eluent for column
chromatography: hexane/EtOAc (15:1).
1H NMR (400 MHz,
CDCl3): δ 8.81 (s, 1H), 8.31 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.4
Hz, 1H), 4.46 (q, J = 7.2 Hz, 2H), 1.44 (t, J = 7.2 Hz, 3H); 19F
NMR (376 MHz, CDCl3): δ -41.08 (s, 3F); 13C NMR (101 MHz,
CDCl3): δ 163.6, 147.7, 134.1, 131.2, 130.6 (q, J = 3.0 Hz),
128.6 (q, J = 312.1 Hz), 126.7, 62.2, 14.2; MS (ESI): m/z 296
[M+H]+; HRMS (ESI-TOF): m/z Calculated for C10H9F3NO4S
[M+H]+: 296.0199; Found: 291.0196.
8. (a) Danoun, G.; Bayarmagnai, B.; Gruenberg, M. F.; Goossen, L.
J. Chem. Sci. 2014, 5, 1312. (b) Bayarmagnai, B.; Matheis, C.;
Risto, E.; Goossen, L. J. Adv. Synth. Catal. 2014, 356, 2343. (c)
Matheis, C.; Wagner, V.; Goossen, L. J. Chem. Eur. J. 2016, 22,
79. (d) Koziakov, D.; Majek, M.; von Wangelin, A. J. Org.
Biomol. Chem. 2016, 14, 11347. (e) Koziakov, D.; Majek, M.; von
Wangelin, A. J. Eur. J. Org. Chem. 2017, 6722. (f) Bertoli, G.;
Exner, B.; Evers, M. V.; Tschulik, K.; Gooßen, L. J. J. Fluorine
Chem. 2018, 210, 132.
Acknowledgments
9. For selected examples, see: (a) Teverovskiy, G.; Surry, D. S.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50, 7312. (b)
Zhang, C.-P.; Vicic, D. A. J. Am. Chem. Soc. 2012, 134, 183. (c)
Weng, Z.; He, W.; Chen, C.; Lee, R.; Tan, D.; Lai, Z.; Kong, D.;
Yuan, Y.; Huang, K. Angew. Chem., Int. Ed. 2013, 52, 1548. (d)
Xu, J.; Mu, X.; Chen, P.; Ye, J.; Liu. G. Org. Lett. 2014, 16, 3942.
(e) Yin, G.; Kalvet, I.; Schoenebeck, F. Angew. Chem., Int. Ed.
2015, 54, 6809. (f) Yin, G.; Kalvet, I.; Englert, U.; Schoenebeck,
F. J. Am. Chem. Soc. 2015, 137, 4164. (g) Zhang, M.; Weng, Z.
Adv. Synth. Catal. 2016, 358, 386. (h) Yang, Y.; Xu, L.; Yu, S.;
Liu, X.; Zhang, Y.; Vicic, D. A. Chem. Eur. J. 2016, 22, 858. (i)
Nguyen, T.; Chiu, W.; Wang, X.; Sattle, M. O.; Love, J. A. Org.
Lett. 2016, 18, 5492. (j) Kalvet, I.; Guo, Q.; Tizzard, G. J.;
Schoenebeck, F. ACS Catal. 2017, 7, 2126.
10. (a) Zhong, W.; Liu, X. Tetrahedron Lett. 2014, 55, 4909. (b) Dürr,
A. B.; Yin, G.; Kalvet, I.; Napoly, F.; Schoenebeck, F. Chem. Sci.
2016, 7, 1076.
11. (a) Liu, J.-B.; Xu, X.-H.; Chen, Z.-H.; Qing, F. L. Angew. Chem.,
Int. Ed. 2015, 54, 897. (b) Nikolaienko, P.; Pluta, R.; Rueping, M.
Chem. Eur. J. 2014, 20, 9867. (c) Glenadel, Q.; Tlili, A.; Billard,
T. Eur. J. Org. Chem. 2016, 1955. (d) Anselmi, E.; Simon, C.;
Marrot, J.; Bernardelli, P.; Schio, L.; Pégot, B.; Magnier, E. Eur.
J. Org. Chem. 2017, 6319. (e) Luo, J.-J.; Zhang, M.; Lin, J.-H.;
Xiao, J.-C. J. Org. Chem. 2017, 82, 11206.
We thank the National Natural Science Foundation of China
(21332010, 21421002), the Strategic Priority Research Program
of the Chinese Academy of Sciences (XDB20000000), and
Youth Innovation Promotion Association CAS (No. 2016234) for
funding this work.
References and notes
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Soc. Rev. 2008, 37, 320. (b) Meanwell, N. A. J. Med. Chem. 2011,
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Supplementary data associated with this article can be found,
in the online version, at doi:XXX/XXX.