Copper(I)-mediated trifluoromethylthiolation of α-bromoketone with element sulfur and (trifluoromethyl)trimethylsilane

Article abstract of DOI:10.1016/j.tet.2015.06.068

A new method has been developed for the copper(I)-mediated trifluoromethylthiolation of α-bromoketone using commercial anhydrous potassium fluoride, elemental sulfur, and (trifluoromethyl)-trimethylsilane in anhydrous N,N-dimethylformamide. This protocol

Full text of DOI:10.1016/j.tet.2015.06.068

Accepted Manuscript
Copper (I)-Mediated Trifluoromethylthiolation of α-Bromoketone with Element Sulfur
and (Trifluoromethyl)trimethylsilane
Jue Li, Fei-Fei Xie, Peiqiang Wang, Qiang-Yong Wu, Wei-Dong Chen, Jiangmeng
Ren, Bu-Bing Zeng
PII:
S0040-4020(15)00965-5
10.1016/j.tet.2015.06.068
TET 26904
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 14 May 2015
Revised Date: 12 June 2015
Accepted Date: 16 June 2015
Please cite this article as: Li J, Xie F-F, Wang P, Wu Q-Y, Chen W-D, Ren J, Zeng B-B,
Copper (I)-Mediated Trifluoromethylthiolation of α-Bromoketone with Element Sulfur and
(Trifluoromethyl)trimethylsilane, Tetrahedron (2015), doi: 10.1016/j.tet.2015.06.068.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Copper(I)-Mediated Trifluoromethylthiolat-
ion of α-Bromoketone with Element Sulfur
and (Trifluoromethyl)trimethylsilane
Leave this area blank for abstract info.
Jue Li a, Fei-Fei Xie a, Peiqiang Wang a, Qiang-Yong Wu a, Wei-Dong Chen b, Jiangmeng Ren a, *, Bu-Bing
Zeng a,b, c, *

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Copper (I)-Mediated Trifluoromethylthiolation of α-Bromoketone with Element
Sulfur and (Trifluoromethyl)trimethylsilane
Jue Li a, Fei-Fei Xie a, Peiqiang Wang a, Qiang-Yong Wu a, Wei-Dong Chen b, Jiangmeng Ren a, , Bu-
Bing Zeng a, b, c,
a Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, PR China
b Shanghai Key Laboratory of Chemical Biology, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, PR China
c Key Laboyatory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling
Road,Shanghai 200032, PR China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A new method has been developed for the copper (I)-mediated trifluoromethylthiolation of α-
bromoketone using commercial anhydrous potassium fluoride, elemental sulfur and
(trifluoromethyl)-trimethylsilane in anhydrous N, N-dimethylformamide. This protocol provides
facile access to a variety of α-trifluoromethylthiolated carbonyl compounds in moderate to
excellent yields under mild and ligand free conditions.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Trifluoromethylthiolation
α-Bromoketone
Sulfur
(Trifluoromethyl)trimethylsilane
1. Introduction
pyrrolidine to give the corresponding trifluoromethyl sulfides in
generally high yields.5 In addition, Weng group reported a
copper-catalyzed α-trifluoromethylthiolation of α-bromoketones
using 1,10-phen as a ligand and S8/TMSCF3 as a SCF3source.6
Because of the strong electron-withdrawing nature and high
hydrophobic domain, the introduction of SCF3 group into small
organic molecules such as pharmaceuticals and agrochemicals
could significantly alter their properties including lipophilicity,
metabolic stability and bioavailability.1 Therefore, employing
new methods for introduction of trifluoromethylthio group into
small organic molecules would be urgently required in synthetic
chemistry.
The above mentioned methods have the issues of either using
toxic and unstable trifluoromethylthiolation reagents or being
longer reaction time. In the current research, a method for
trifluoromethylthiolation of α-bromoketones was developed
under a mild and ligand free condition in a relatively short time
to give the corresponding trifluoromethyl sulfides in moderate to
excellent yields.
In 1973, Haas firstly reported the synthesis of α-trifluoro-
methylthiolated kotones starting from ketones using trifluoro-
methylsulfenyl chloride as the trifluoromethylthiolation reagent. 2
Then, in 1987, Kolasa reported the α-trifluoromethylthiolation of
benzoylacetic ethyl esters using trifluoromethylsulfenyl chloride
2. Results/Discussion
Previously, our research group reported the new
trifluoromethylthiolation method of allylic halides.7 It was found
when α-bromoacetophenone was subjected to the same condition,
the corresponding α-trifluoromethylthioacetophenone was
obtained in 28.7 % yield. Encouraged by this result, a series of
copper salts were screened in which CuI gave the best result
(Table 1, Entry 3). Additional screening of bases indicated that
replacement of KF with K2CO3, Na2CO3, Et3N or DBU could not
let this reaction happen and using CsF only gave the product in
as well.3
Recently, Shen and Rueping reported the α-
trifluoromethylthiolation of β-ketoesters independently to give
trifluoromethylthiolated carbonyl compounds with good stero-
selectivity.4 Zard group reported a new trifluoromethylthiolation
reagent, O-octadecyl-S-trifluorothiolcarbonate, which could be
prepared in two steps from trifluoroacetic anhydride and sodium
O-octadecyl-dithiocarbonate. This reagent reacts directly with α-
bromoketones in the presence of potassium fluoride and
———
Corresponding author. Tel.: +0-021-642-52199; e-mail: renjm@ecust.edu.cn
Corresponding author. Tel.: +0-021-642-53689; e-mail: zengbb@ ecust.edu.cn

2
Tetrahedron
ACCEPTED MANUSCRIPT
8.0% yield. It was noteworthy that when the reaction was
(Table 1, Entry 10). Following on these preliminary results, the
conducted in the absence of CuI, the yield was quite low (Table
1, Entry 9). Furthermore, no product was observed without KF
which indicated that this base was essential for the reaction
molar equivalency of CuI and KF was investigated. The results
indicated that changing the molar equivalency of CuI and KF
would cause the decline of the yields.
Table 1. Optimization of reaction conditionsa
Table 2. Scope of different substratesa
Entry
1
Cu salt (equiv.)
CuSCN (0.5)
Base (equiv.)
KF (4.0)
Yield (%)b
28.7
Entry Substrate
1
Product
Yield(%)b
92.5
2
3
4
CuCl (0.5)
CuI (0.5)
CuBr (0.5)
KF (4.0)
KF (4.0)
KF (4.0)
73.7
92.5
58.9
5
6
7
8
CuCl2(0.5)
Cu(OAc)2 (0.5)
Cu (0.5)
CuI (0.5)
-
CuI (0.5)
CuI (0.1)
CuI (0.2)
CuI (0.3)
CuI (1.0)
CuI (0.5)
CuI (0.5)
KF (4.0)
KF (4.0)
KF (4.0)
CsF (4.0)
KF (4.0)
-
KF (4.0)
KF (4.0)
KF (4.0)
KF (4.0)
KF (3.0)
KF (2.0)
16.1
51.0
23.9
8.0
28.4
NRc
38.7
64.6
76.3
trace
79.2
75.2
2
3
83.2
60.6
9
10
11
12
13
14
15
16
a Reaction conditions: 1a (2.0 mmol), copper salt, base, S8 (6.0 mmol) and
4
5
6
70.2
78.0
66.2
TMSCF3 (6.0 mmol) in anhydrous DMF under N2 at room temperature.
b Isolated yield.
c NR = No reaction.
Based on these, 0.5 equiv. of CuI and 4.0 equiv. of KF would be
the optimal conditions.
With the optimal condition in hand, the research was extent
further to investigate the substrate scope of this reaction. Firstly,
a series of α-bromoketones with different substituents at various
positions of the phenyl ring were investigated. The results
declared that both steric hindrance and electron density had an
impact on the reaction. On the one hand, from the perspective
view of steric hindrance, any para-substituent substrate gave the
highest yield while the ortho-substituent substrate gave the
lowest (Entries 2 and 3). On the other hand, from the perspective
view of electron density, compounds bearing electron-donating
group (Entries 2-4) gave higher yields than those bearing
electron-withdrawing ones at the same position (Entries 7-9).
Obviously, only 60.6 % of the product was obtained from
substrate 1c and even no product was detected with substrate 1g
(Table 2, Entries 3 and 7). It is noteworthy that, compounds with
strong electron-withdrawing substituents gave the corresponding
products in an extremely low yield or even failed to react (Entries
11 and 13). This condition equally applied to α-bromopropio-
phenones to give corresponding trifluoromethylthiolated products
in moderate to good yields (Entries 14-16). α-Bromoaceto-
naphthone 1q could also reacted smoothly under the optimized
condition to give the desired product 2q in 79.8 % yield (Entry
17). Similarly, the optimized condition could also work on the
aliphatic alkane 1r to give the corresponding product in 65.6 %
yield (Entry 18).
7
8
NDc
67.3
52.9
O
Br
Cl
1h
9
10
72.0

3
S
11
12
16.4
ACCEPTED MANUSCRIPT
H
S8 + DMF
CF3
N
KF, DMF
TMSCF3
SCF3
Ref. 8
SCN
CuI
CuSCN
62.5
F3CS
SCF3
A
O
O
R
Br
SCF3
2a
R
1a
13
14
NDc
77.4
O
Br
F3CS
Br
CuIII
SCN
F3CS
O
R
O2N
B
1m
Scheme1. Proposed Mechanism
15
80.2
3. Conclusion
In conclusion, an efficient and convenient method for the
synthesis of series of α-trifluoromethylthioketones was
a
developed. This protocol proceeds without any ligand under a
mild condition and short reaction time to expressly provide the
corresponding products in moderate to excellent yields. Notably,
all the reagents used in the reaction are inexpensive and nontoxic.
16
17
62.5
79.8
4. Experimental section
4.1. General
Unless stated otherwise, all reagents and solvents were obtained
from commercial sources without purification. Column
chromatography was carried out on silica gel (200-300 ꢀm).
Melting points were determined using a digital melting-point
apparatus and are uncorrected. 1H NMR, 13C NMR and 19F NMR
spectra were recorded on a spectrometer (400 MHz, 100 MHz
and 376 MHz or 500 MHz, 125 MHz and 470 MHz) using
TMS as internal standard. HRMS data were determined by EI
ionization.
18
19
65.6
70.3
General Procedure: To an oven-dried Schlenk flask were
charged with CuI (0.5 eq.), anhydrous KF (4.0 eq.) and S8 (3.0
eq.) under N2. Then, the solution of substrate (2.0 mmol) in
DMF(12 mL) and TMSCF3 (0.9 mL 3.0 eq.) were added
successively via syringe. After that, the reaction mixture was
stirred at room temperature for 10 min. Water was added and the
mixture was filtered through celite. The resulting filtrate was
extracted three times with ethyl acetate, and the combined
organic layers were washed with water and dried over anhydrous
sodium sulfate. The solvent was removed by rotary evaporation
and the residue was purified by column chromatography on silica
gel with petroleum ether and ethyl acetate.
a Reaction conditions: 1 (2.0 mmol), CuI (1.0 mmol), KF (8.0 mmol), S8 (6.0
mmol) and TMSCF3 (6.0 mmol) in anhydrous DMF under N2 at room
temperature.
b Isolated yield.
c ND = Not detected.
Based on the previous research work,7 a reaction mechanism
was proposed as below (Scheme 1). Firstly, TMSCF3 was
converted to an active SCF3 anion in the presence of KF, S8 and
DMF, which was then reacted with CuSCN to give copper (I)
complex A. Then, substrate 1a reacted with the resulting copper
(I) complex to give a copper (III) complex B which then reacted
to give product 2a together with complex A to complete the
reaction circle.
4.2. 1-Phenyl-2-((trifluoromethyl)thio)ethanone (2a)
1
Colorless oil, yield 92.5 %; H NMR (400 MHz, CDCl3) δ 7.96
(dd, J = 8.0, 1.4 Hz, 2H), 7.64 (tt, J = 8.0, 1.4 Hz, 1H), 7.52 (t, J
= 8.0 Hz, 2H), 4.52 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
192.0, 134.7, 134.3, 130.7 (q, JC-F = 304.4 Hz), 129.0,128.4,
38.4; 19F NMR (376 MHz, CDCl3) δ -41.44 (s, 3F). HRMS (EI)
calcd. for C9H7F3OS: 220.0170, found 220.0135.
4.3. 1-(p-Tolyl)-2-((trifluoromethyl)thio)ethanone (2b)
1
Yellow oil, yield 83.2 %; H NMR (400 MHz, CDCl3) δ 7.84 (d,
J = 8.2 Hz, 2H), 7.30 (d, J = 8.2 Hz, 2H), 4.49 (s, 2H), 2.43 (s,

4
Tetrahedron
1
3H); 13C NMR (100 MHz, CDCl3) δ 191.6, 145.4, 132.2, 130.8
Yellow oil, yield 16.4 %; H NMR (500 MHz, CDCl3) δ 8.06 (d,
J = 8.4 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 4.50 (s, 2H); 13C NMR
(125 MHz, CDCl3) δ190.9, 137.5, 132.8, 130.3 (q, JC-F = 305.0
Hz), 128.9, 117.6, 117.5, 38.1; 19F NMR (470 MHz, CDCl3) δ -
41.37 (s, 3F); HRMS (EI) calcd. for C10H6F3NOS: 245.0122,
found 245.0121.
ACCEPTED MANUSCRIPT
(q, JC-F = 304.5 Hz), 129.7, 128.5, 38.4 (q, JC-F = 1.8 Hz), 21.7;
19F NMR (376 MHz, CDCl3) δ -41.45 (s, 3F). HRMS (EI) calcd.
for C10H9F3OS: 234.0326, found 234.0329.
4.4. 1-(o-Tolyl)-2-((trifluoromethyl)thio)ethanone (2c)
Yellow oil, yield 60.6 %; 1H NMR (500 MHz, CDCl3) δ 7.68 (dd,
J = 6.8, 1.6 Hz, 1H), 7.45 (td, J = 7.6, 1.2 Hz, 1H), 7.31 (t, J =
6.8 Hz, 2H), 4.46 (s, 2H), 2.54 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 194.8, 139.8, 134.6, 132.7, 132.6, 130.7 (q, JC-F = 304.4
Hz), 129.1, 126.0, 40.4, 21.6; 19F NMR (470 MHz, CDCl3) δ -
41.36 (s, 3F); HRMS (EI) calcd. for C10H9F3OS: 234.0326, found
234.0327.
4.13. 1-(4-(Trifluoromethyl)phenyl)-2-((trifluoromethyl)thio)-
ethanone (2l)
1
Colorless oil, yield 62.5 %; H NMR (400 MHz, CDCl3) δ 8.07
(d, J = 8.2 Hz, 2H), 7.78 (d, J = 8.2 Hz, 2H), 4.52 (s, 2H); 13C
NMR (100 MHz, CDCl3) δ 191.3, 137.3, 135.5 (q, JC-F = 32.7
Hz), 130.4 (q, JC-F = 304.8 Hz), 128.8, 126.1 (q, JC-F = 3.6 Hz),
123.3 (q, JC-F = 271.2 Hz), 38.2 (q, JC-F = 1.6 Hz); 19F NMR (376
MHz, CDCl3) δ -41.46 (s, 3F), -63.35 (s, 3F). HRMS (EI) calcd.
for C10H6F6OS: 288.0044, found 288.0046.
4.5. 1-(m-Tolyl)-2-((trifluoromethyl)thio)ethanone (2d)
1
Yellow oil, yield 70.2 %; H NMR (500 MHz, CDCl3) δ 7.76 (s,
1H), 7.74 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 8.0 Hz, 1H), 7.39 (t, J
= 8.0 Hz, 1H), 4.51 (s, 2H), 2.43 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 192.2, 139.0, 135.1, 134.8, 130.7 (q, JC-F = 304.6 Hz),
128.9, 128.8, 125.6, 38.5, 21.3; 19F NMR (470 MHz, CDCl3) δ -
41.41 (s, 3F); HRMS (EI) calcd. for C10H9F3OS: 234.0326, found
234.0325.
4.15. 1-Phenyl-2-((trifluoromethyl)thio)propan-1-one (2n)
1
Colorless oil, yield 77.4 %; H NMR (500 MHz, CDCl3) δ 7.97
(d, J = 7.6 Hz, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.51 (t, J = 7.6 Hz,
2H), 4.99 (q, J = 7.0 Hz, 1H), 1.73 (d, J = 7.0 Hz, 3H); 13C NMR
(125 MHz, CDCl3) δ 196.3, 134.1, 134.0, 133.7, 130.8 (q, JC-F
=
305.4 Hz), 129.0, 128.7, 44.5 (q, JC-F = 0.9 Hz), 41.5; 19F NMR
(470 MHz, CDCl3) δ -39.78 (s, 3F). HRMS (EI) calcd. for
C10H9F3OS: 234.0326, found 234.0327.
4.6. 1-(3-Methoxyphenyl)-2-((trifluoromethyl)thio)ethanone (2e)
1
Colorless oil, yield 78.0 %; H NMR (400 MHz, CDCl3) δ 7.52
(dt, J = 8.0, 1.0 Hz, 1H), 7.48 (m, 1H), 7.42 (t, J = 8.0 Hz, 1H),
7.18 (ddd, J = 8.0, 2.4, 1.0 Hz, 1H), 4.51 (s, 2H), 3.87 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 191.8, 160.1, 136.0, 130.7 (q, JC-F
= 304.3 Hz), 130.0, 121.0, 120.7, 112.7, 55.5, 38.4 (q, JC-F = 1.9
Hz); 19F NMR (376 MHz, CDCl3) δ -41.43 (s, 3F). HRMS (EI)
calcd. for C10H9F3O2S: 250.0275, found 250.0276.
4.16. 1-(p-Tolyl)-2-((trifluoromethyl)thio)propan-1-one (2o)
1
Colorless oil, yield 80.2 %; H NMR (500 MHz, CDCl3) δ 7.87
(d, J = 8.5 Hz, 2H), 7.31 (d, J = 8.5 Hz, 2H), 4.97 (q, J = 7.2 Hz,
1H), 2.44 (s, 3H), 1.71 (d, J = 7.2 Hz, 3H); 13C NMR (125 MHz,
CDCl3) δ 195.9, 145.2, 131.4, 130.8 (q, JC-F = 305.1), 129.7,
128.9, 44.5, 21.7, 19.9; 19F NMR (470 MHz, CDCl3) δ -39.81 (s,
3F); HRMS (EI) calcd. for C11H11F3OS: 248.0483, found
248.0481.
4.7. 1-(4-Bromophenyl)-2-((trifluoromethyl)thio)ethanone (2f)
Yellow oil, yield 66.2 %; 1H NMR (400 MHz, CDCl3) δ 7.82 (dt,
J = 8.8, 2.0 Hz, 2H), 7.66 (dt, J = 8.8, 2.0 Hz, 2H), 4.46 (s, 2H);
13C NMR (100 MHz, CDCl3) δ 191.1, 133.4, 132.4, 130.5 (q, JC-F
= 304.7 Hz), 129.9, 129.7, 38.1 (q, JC-F = 1.9 Hz); 19F NMR (376
4.17. 1-(4-Fluorophenyl)-2-((trifluoromethyl)thio)propan-1-one
(2p)
1
Colorless oil, yield 62.5 %; H NMR (500 MHz, CDCl3) δ 8.01
MHz, CDCl3)
δ -41.41 (s, 3F). HRMS (EI) calcd. for
(m, 2H), 7.19 (m, 2H), 4.92 (q, JC-F = 7.0 Hz, 1H), 1.72 (d, JC-F
=
C9H6BrF3OS: 297.9275, found 297.9270.
7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 194.7, 167.3, 165.3,
131.5, 131.4, 130.7 (q, JC-F = 305.3 Hz), 116.3, 116.1, 44.2, 19.6;
19F NMR (470 MHz, CDCl3) δ -39.81 (s, 3F); HRMS (EI) calcd.
for C10H8F4OS: 252.0232, found 252.0232.
4.9. 1-(4-Chlorophenyl)-2-((trifluoromethyl)thio)ethanone (2h)
1
Yellow oil, yield 67.3 %; H NMR (500 MHz, CDCl3) δ 7.90 (d,
J = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 4.48 (s, 2H); 13C NMR
(125 MHz, CDCl3) δ 190.9, 140.9, 133.0, 130.6 (q, JC-F = 304.7
Hz), 129.8, 129.4, 38.2 (q, JC-F = 1.9 Hz); 19F NMR (470 MHz,
CDCl3) δ -41.42 (s,3F). HRMS (EI) calcd. for C9H6ClF3OS:
253.9780, found 253.9777.
4.18. 1-(Naphthalen-1-yl)-2-((trifluoromethyl)thio)ethanone (2q)
Colorless oil, yield 79.8 %;1H NMR (500 MHz, CDCl3) δ 8.69
(d, J = 9.0 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.91 (t, J = 8.5 Hz,
2H), 7.64 (m, 1H), 7.57 (m, 1H), 7.52 (t, J = 7.5 Hz, 1H), 4.59 (s,
2H); 13C NMR (125 MHz, CDCl3) δ 195.0, 134.4, 134.1, 132.5,
130.7 (q, JC-F = 304.8), 130.3, 128.8, 128.7, 128.6, 126.9, 125.6,
124.2, 40.6; 19F NMR (470 MHz, CDCl3) δ -41.30 (s, 3F);
HRMS (EI) calcd. for C13H9F3OS: 270.0326, found 270.0325.
4.10. 1-(3-Chlorophenyl)-2-((trifluoromethyl)thio)ethanone (2i)
1
Yellow oil, yield 52.9 %; H NMR (400 MHz, CDCl3) δ 7.92 (s,
1H), 7.83 (d, J = 8.0 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.46 (t, J
= 8.0 Hz, 1H), 4.48 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
190.9, 136.2, 135.4, 134.2, 130.5 (q, JC-F = 304.8), 130.3, 128.4,
126.5, 38.2; 19F NMR (376 MHz, CDCl3) δ -41.43 (s, 3F).
HRMS (EI) calcd. for C9H6ClF3OS: 253.9780, found 253.9781.
4.19. 1-((Trifluoromethyl)thio)undecan-2-one (2r)
1
Yellow oil, yield 65.6 %; H NMR (500 MHz, CDCl3) δ 3.80 (s,
2H), 2.57 (t, J = 7.5 Hz, 2H), 1.62 (m, 2H), 1.27 (m, 12H), 0.88
(t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 202.9, 130.5
(q, JC-F = 304.8 Hz), 41.3, 40.1, 31.8, 29.4, 29.3, 29.2, 29.0, 23.7,
22.7, 14.1; 19F NMR (470 MHz, CDCl3) δ -41.67 (s, 3F); HRMS
(EI) calcd. for [C12H21F3OS+H]: 271.1343, found 271.1338.
4.11. 1-(4-Fluorophenyl)-2-((trifluoromethyl)thio)ethanone (2j)
1
Colorless oil, yield 72.0 %; H NMR (400 MHz, CDCl3) δ 8.00
(m, 2H), 7.19 (m, 2H), 4.49 (s, 2H); 13C NMR (100 MHz, CDCl3)
δ 190.5, 167.7, 165.1, 131.3, 131.2, 130.6 (q, JC-F = 304.7),
116.4, 116.1, 38.2 (q, JC-F = 1.6Hz); 19F NMR (376 MHz, CDCl3)
δ -41.43 (s, 3F). HRMS (EI) calcd. for C9H6F4OS: 238.0075,
found 238.0076.
4.20. 1-((trifluoromethyl)thio)tridecan-2-one (2s)
1
Yellow solid, yield 70.3 %; H NMR (500 MHz, CDCl3) δ 3.82
(s, 2H), 2.58 (t, J = 7.5 Hz, 2H), 1.61 (m, 2H), 1.26 (m, 16H),
4.12. 4-(2-((Trifluoromethyl)thio)acetyl)benzonitrile (2k)

5
0.88 (t, J = 6.7 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 202.5,
ACCEPTED MANUSCRIPT
130.0 (q, JC-F = 304.6 Hz), 40.7, 39.6, 31.5, 29.1, 29.0, 28.9,
28.8, 28.6, 23.2, 22.2, 13.6; 19F NMR (470 MHz, CDCl3) δ -
41.72 (s, 3F); HRMS (EI) calcd. for C14H25F3OS: 298.1578,
found 298.1578.
Acknowledgements
We thank the National Natural Science Foundation of China
(21302053) for the generous financial support. We are also
grateful for the financial support from the Fundamental Research
Funds for the Central University (WY111307).
Supplementary data
1H, 13C and 19F NMR data associated with this article.
References and notes
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Kondratenko, N. V. Russ.Chem. Rev. 1974, 43, 32-47. (f) Tlili, A.;
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ACCEPTED MANUSCRIPT
Copper (I)-Mediated Trifluoromethylthiolation of α-Bromoketone
with Element Sulfur and (Trifluoromethyl)trimethylsilane
Jue Li a, Fei-Fei Xie a, Qiang-Yong Wu a, Jiangmeng Ren a, *, Bu-Bing Zeng a, b, *
a Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, PR China
b Key Laboyatory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Lingling Road,Shanghai 200032, PR China.
Fax +86(21)64253689; E-mail: renjm@ecust.edu.cn;zengbb@ecust.edu.cn
Supporting information
Table of Contents
Copies of 1H, 13C and 19F NMR Spectra
S2-27
S1

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Copies of 1H , 13C and 19F NMR Spectra.
Compound 2a
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Compound 2b
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Compound 2c
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Compound 2d
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Compound 2e
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Compound 2f
S9

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Compound 2h
S11

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Compound 2i
S12

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S13

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Compound 2j
S14

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Compound 2k
S15

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S16

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Compound 2l
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Compound 2n
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S19

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Compound 2o
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Compound 2p
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Compound 2q
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