Copper-catalyzed trifluoromethylation of arylsulfinate salts using an electrophilic trifluoromethylation reagent

Article abstract of DOI:10.1016/j.tet.2013.01.041

A copper-catalyzed method for the trifluoromethylation of arylsulfinates with Togni's reagent has been developed, affording aryltrifluoromethylsulfones in moderate to good yields. A wide range of functional groups in arylsulfinates are compatible with the

Full text of DOI:10.1016/j.tet.2013.01.041

Tetrahedron 69 (2013) 2628e2632
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Copper-catalyzed trifluoromethylation of arylsulfinate salts using an
electrophilic trifluoromethylation reagent
,
Xiaoxi Lin a b, Guimei Wang a, Huaifeng Li c, Yuanyuan Huang a, Weiming He a,
,
a
a,b,
*
Dandan Ye a, Kuo-Wei Huang c , Yaofeng Yuan , Zhiqiang Weng
*
a Department of Chemistry, Fuzhou University, Fujian 350108, PR China
b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou,
Fujian 350002, PR China
c King Abdullah University of Science and Technology (KAUST), Division of Physical Sciences and Engineering and KAUST Catalysis Center,
Thuwal 23955-6900, Saudi Arabia
a r t i c l e i n f o
a b s t r a c t
Article history:
A copper-catalyzed method for the trifluoromethylation of arylsulfinates with Togni’s reagent has been
developed, affording aryltrifluoromethylsulfones in moderate to good yields. A wide range of functional
groups in arylsulfinates are compatible with the reaction conditions.
Received 29 October 2012
Received in revised form 28 December 2012
Accepted 15 January 2013
Ó 2013 Elsevier Ltd. All rights reserved.
Available online 25 January 2013
Keywords:
Copper catalyst
Electrophilic trifluoromethylation reaction
Aryltrifluoromethylsulphones
1. Introduction
trimethylsilane and (trifluoromethyl)-trimethylstannane.8 Despite
these procedures being attractive for their simplicity, some limita-
Fluorinated aromatic molecules have important applications in
the pharmaceutical, agricultural, and advanced materials in-
dustries.1 In medicinal chemistry, the incorporations of fluorine
containing substituents, such as F, CF3, SCF3, OCF3, and SO2CF3 to
a target molecule could dramatically improve their binding selec-
tivity, metabolic stability, and lipophilicity.
Aryltrifluoromethylsulfones are frequently used as important
structural motifs in bioactive compounds,2 chiral catalysts,3 and
functional materials.4 They can also serve as important precursors to
many other chemicals, such as various trifluoromethylated com-
pounds5 or aryl sulfones.6 However, relatively few synthetic ap-
proaches for the preparation of aryltrifluoromethylsulfones are
currently available. The commonly known methods for the synthesis
of aryltrifluoromethylsulfones are the oxidation of corresponding
aryl trifluoromethylsulphides.7 Notably, Yagupolski and co-workers
have reported a one-pot procedure for the fluoride-catalyzed cross-
coupling of arenesulfonyl fluorides with (trifluoromethyl)
tions still remain, e.g., they are incompatible with some functional
groups; the sulfides are not easily available;8 and the yields and se-
lectivity are poor.
A flourish of activity in the development of metal-mediated and
catalyzed trifluoromethylation reactions has been recently wit-
nessed in the literature,9,10 using either nucleophilic or electrophilic
trifluoromethylating reagents, such as the RuppertePrakash’s re-
agent (TMSCF3)11 or its ethyl derivative,12 fluoroform,13 potassium
(trifluoromethyl)trimethoxyborate,14 Togni’s reagent,11a,15 Ume-
moto’s reagent,16 and the (trifluoromethyl)diphenylsulfonium salt
as CF3 sources.17
Our laboratories have initiated research programs aimed at the
developmentofcopper-catalyzed trifluoromethylation reactions.11a,18
As part of the efforts of these programs, we sought to develop an ef-
fective route for the synthesis of aryltrifluoromethylsulfones through
copper-catalyzed trifluoromethylation. Due to their stable nature,
readily availability, and easiness to handle, sulfinic acid sodium salts
have the potential to serve as an ideal arenesulfone source for the
preparation of aryltrifluoromethylsulfones via trifluoromethylation.
Herein, we report a copper-catalyzed cross-coupling reaction of
arylsulfinate salts with Togni’s reagent.
* Corresponding authors. Tel.: þ966 28080328 (K.W.H.); tel./fax: þ86
59122866121 (Z.W.); e-mail addresses: hkw@kaust.edu.sa (K.-W. Huang), zweng@
fzu.edu.cn (Z. Weng).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.01.041

X. Lin et al. / Tetrahedron 69 (2013) 2628e2632
2629
2. Results and discussion
naphthyl sulfinate sodium salts afforded the trifluoromethylate
products in good yields (Table 2, entries 7 and 8). Notably, a wide
range of functional groups, including methoxy, cyano, nitro, fluoro,
and heteroaryl groups, are well tolerated under the present re-
action conditions (Table 2, entries 9e13). Substrates bearing
electron-donating groups, such as 4-methoxybenzenesulfinate,
could also be employed to provide the corresponding product in
acceptable yields (Table 2, entry 9). To achieve an effective tri-
fluoromethylation of m-nitro benzenesulfinate, we optimized the
reaction conditions again. Replacement of Cu(OTf)2/L3 with
Cu(TFA)2/L1 led to a good yield of product (Table 2, entry 11). It
should be mentioned that pharmaceutically interesting functional
groups, such as heteroaryl groups were also completely compatible.
Thereby, reaction of 8-quinoline sulfinate catalyzed by CuPF6
We chose to examine our strategy by screening the tri-
fluoromethylation reactions of benzenesulfinate sodium salts
(Table 1). Various copper precursors, bidentate ligands, solvents,
reaction temperatures, and time were evaluated for the reaction of
1a with Togni’s reagent (1-trifluoromethyl-1,2-benziodoxol-3-
(1H)-one (2a) and 1-trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-
benziodoxole (2b)).1g,19 After considerable effort, we identified that
formation of the (trifluoromethylsulfonyl)benzene product 3a
could be achieved in good yield (78%) when the reaction was
conducted with a combination of Cu(TFA)2 (TFA¼trifluoroacetate),
phenanthroline (L1), and tetrabutylammonium fluoride (Table 1,
entry 1).
Table 1
Optimization of copper-catalyzed trifluoromethylation of sulfinate saltsa
Yieldb (%)
þ
Entry
[Cu]
Ligand
CF3 reagent
Solvent
Time (h)
Bu4NF (equiv)
Temp (ꢀC)
1
2
3
4
5
6
7
8
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cul
Cu(OTf)2
Cu(MeCN)4PF6
None
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
L1
L1
L1
L1
L1
L1
L1
None
L2
L3
L1
L1
L1
L1
2a
2b
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
THF
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
15
0.5
0.5
None
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
130
130
130
90
130
130
130
130
130
130
130
60
78
36
37
19
32
45
45
19
40
43
61
7
9
10
11
12
13
14
8.5
8.5
8.5
CH2CI2
CH3CN
40
80
6
3
a
Reaction conditions: 1a (0.10 mmol), 2 (0.25 mmol), solvent (2.0 mL), under Ar atmosphere.
Yields were determined by GC analysis of the crude reaction mixture with an internal standard.
b
Variation of the trifluoromethylation reagents showed that 2a is
(CH3CN)4/L3 rather than Cu(TFA)2/L1, afforded the tri-
fluoromethylate product in good yields (Table 2, entry 13).
A plausible catalytic cycle for the present trifluoromethylation
reaction is depicted in Scheme 1. First a bipyridine ligated (N,N)
Cu(TFA)2 complex (A), generated in situ, undergoes the trans-
metallation reaction with sodium arylsulfinate to give a copper(II)
intermediate B. Subsequently, the nucleophilic attack of the ArSO2
group of B to the CF3þmoiety in the Togni’s reagent affords the
trifluoromethylation product ArSO2CF3 along with the cop-
perebenzoate complex (C). Finally, C reacts with sodium arylsul-
finate to regenerate B to complete the catalytic cycle.
superior to 2b (Table 1, entry 2). Importantly, in the absence of either
of the copper species/ligands, or Bu4NF, the reaction efficiency was
significantly decreased (Table 1, entries 3 and 8) as did lowering the
reaction temperature (Table 1, entry 4). A subsequent screening of
copper sources, i.e., CuI, Cu(OTf)2, and Cu(MeCN)4PF6 with phen (L1)
astheligand,resultedinloweryields(Table 1, entries5e7). Thenature
of the ligand also influences the yields of the trifluoromethylation
products (Table 1, entries 9 and 10). A longer reaction time led to
a significantly lower yield, presumably due to decomposition of the
product (Table 1, entry 11). The choice of solvents proved crucial for
the formation of 3a. The use of THF, CH2Cl2, and CH3CN at reflux re-
tarded the formation of the product (Table 1, entries 12e14).
3. Conclusions
To explore the substrate scope, we examined a range of sulfinate
sodium salts in the trifluoromethylation with 2a under the opti-
mized reaction conditions (Table 2). Reactions with 1a as well as
methyl- and tert-butyl-substituted phenyl sulfinate sodium salts
proceeded well to give good yields of the desired products in
70e76% yield (Table 2, entries 1e3 and 5), although in the case of p-
methyl phenyl sulfinate, Cu(OTf)2 was applied instead of Cu(TFA)2.
The 4-i-propylphenyl and biphenyl sulfinate sodium give slightly
lower yields (Table 2, entries 4 and 6), while both of the 1- and 2-
In summary, we have developed an efficient copper-catalyzed
protocol for the trifluoromethylation of arylsulfinates to synthe-
size aryltrifluoromethylsulfones. A wide variety of functional
groups in arylsulfinates are compatible with the reaction condi-
tions and the aryltrifluoromethylsulfone products have been ob-
tained in good yields. This reaction expands the scope of Cu-
catalyzed electrophilic trifluoromethylation reactions and should
lead to future synthetic applications.

2630
X. Lin et al. / Tetrahedron 69 (2013) 2628e2632
Table 2 (continued)
Table 2
Copper-catalyzed trifluoromethylation of sulfinate salts with Togni’s reagenta
Entry
[Cu]
Ligand
Product
Yield (%)b
13
CuPF6(CH3CN)4
L1
81c
Entry
1
[Cu]
Ligand
Product
Yield (%)b
71
a
Reaction conditions: sulfinate salts (0.50 mmol), 2a (1.25 mmol), [Cu]
(0.10 mmol), phen (0.20 mmol), Bu4NF (0.25 mmol), DMSO (10 mL), 130 ꢀC, under Ar
atmosphere.
Cu(TFA)2
L1
b
Isolation yield.
CsF (1.0 mmol) was added.
c
2
3
Cu(OTF)2
Cu(TFA)2
L1
L1
70
76
4
5
Cu(TFA)2
Cu(TFA)2
L1
L1
51
71
6
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
Cu(TFA)2
L1
L1
L1
L1
L1
60
77
76
41
88
7
Scheme 1. Plausible mechanism.
8
4. Experimental
4.1. General experimental
All solvents were purified by standard methods. 1H, 19F, and 13
C
9
NMR spectra were recorded using BrukerA VIII 400 or AVIII 500
spectrometer. 1H and 13C NMR chemical shifts were reported in
parts per million (ppm) downfield from tetramethylsilane and 19F
NMR chemical shifts were determined relative to CFCl3 as external
standard. Coupling constants (J) are reported in Hertz (Hz). The
residual solvent peak was used as an internal reference: 1H NMR
10
(chloroform
d d 77.0). The fol-
7.26) and 13C NMR (chloroform
lowing abbreviations were used for the multiplicities: s: singlet, d:
doublet, t: triplet, q: quartet, m: multiplet, and br: broad. Column
chromatography purifications were performed by flash chroma-
tography using Merck silica gel 60. The substrates of sodium
benzenesulfinate and sodium p-toluenesulfinate were purchased
from commercial sources and used without further purification.
Other sodium sulfinates were prepared according to literature
procedures.20 Solvents were freshly dried and degassed according
to the procedures in Purification of Laboratory Chemicals prior
to use.
11
12
Cu(OTF)2
Cu(TFA)2
L3
L1
75
38

X. Lin et al. / Tetrahedron 69 (2013) 2628e2632
2631
4.2. General procedure for the copper-catalyzed tri-
fluoromethylation of arylsulfinate salts
7.89 (d, J¼8.4 Hz, 2H), 7.67e7.65 (m, 2H), 7.57e7.50 (m, 3H). 19F NMR
(470 MHz, CDCl3):
d
ꢂ78.60 (s, 3F). 13C NMR (126 MHz, CDCl3):
d
149.6, 138.4, 131.3, 129.6, 129.4, 129.3, 128.4, 127.6, 119.9 (q,
In a glovebox, arylsulfinate salts (0.50 mmol), [Cu] (0.10 mmol),
phen (0.20 mmol), Bu4NF (0.25 mmol), and electrophilic tri-
fluoromethylating reagent (1.25 mmol) were added to an oven-
dried resealable Schlenk tube possessing a Teflon screw valve.
Freshly distilled DMSO (10.0 mL) was added into this tube and the
tube was sealed. The solution was stirred in a preheated (130 ꢀC) oil
bath for 8 h. The reaction mixture was then allowed to cool to room
temperature and passed through a short silica gel pad to remove
metal salts. Water (10.0 mL) was added to the mixture at 0 ꢀC. The
resulting mixture was extracted with diethyl ether (6.0 mLꢁ2), and
the combined organic layers were washed with water (6.0 mLꢁ2),
and then dried over magnesium sulfate. The solvent was removed
by rotary evaporation in an ice bath and the resulting product was
purified by column chromatography on silica gel with pentane.
J¼323 Hz). GCeMS m/z 286 (Mþ). HRMS (EI) m/z: calcd for [M]þ:
C13H9F3O2S: 286.0275; found: 286.0274. IR (KBr) n 3034, 2919, 1723,
1591, 1361, 1213, 1138, 1071, 764, 675 cmꢂ1
.
4.2.7. 1-(Trifluoromethylsulfonyl)naphthalene23 (Table 2, entry 7).
Obtained as a yellow oil in 76% yield (99.4 mg). Rf (5% Et2O/pen-
tane): 0.43. 1H NMR (500 MHz, CDCl3):
d
8.84 (d, J¼8.7 Hz, 1H), 8.50
(dd, J¼7.5, 1.2 Hz, 1H), 8.33 (d, J¼8.2 Hz, 1H), 8.04 (d, J¼8.2 Hz, 1H),
7.82e7.76 (m, 1H), 7.74e7.68 (m, 2H). 19F NMR (470 MHz, CDCl3):
d
ꢂ77.80 (s, 3F). 13C NMR (126 MHz, CDCl3):
d 138.4, 135.2, 134.3,
130.2, 129.7, 129.3, 127.7, 126.9, 124.5, 124.4, 120.3 (q, J¼323 Hz).
GCeMS m/z 260 (Mþ).
4.2.8. 2-(Trifluoromethylsulfonyl)naphthalene (Table 2, entry
8). Obtained as a white solid in 76% yield (98.5 mg); mp 55e57 ꢀC.
4.2.1. Trifluoromethyl phenylsulfone5d,7d (Table 2, entry 1). Obtained
as a colorless oil in 71% yield (74.6 mg). Rf (5% Et2O/pentane): 0.33.
Rf (5% Et2O/pentane): 0.43. 1H NMR (500 MHz, CDCl3):
d 8.69 (s,1H),
8.16e8.07 (m, 2H), 8.03 (d, J¼8.2 Hz, 1H), 7.98 (d, J¼9.8 Hz, 1H), 7.81
1H NMR (500 MHz, CDCl3):
d
8.08 (d, J¼7.8 Hz, 2H), 7.88 (t, J¼7.8 Hz,
(t, J¼7.6 Hz, 1H), 7.74 (t, J¼7.6 Hz, 1H). 19F NMR (470 MHz, CDCl3):
1H), 7.72 (t, J¼7.8 Hz, 2H). 19F NMR (470 MHz, CDCl3):
d
ꢂ78.42 (s,
d
ꢂ78.18 (s, 3F). 13C NMR (126 MHz, CDCl3):
d 136.6, 134.1, 132.1,
3F). 13C NMR (126 MHz, CDCl3):
d
131.8, 126.7, 126.0, 125.1, 115.0 (q,
130.9, 130.2, 129.9, 128.4, 128.2, 128.1, 123.8, 120.0 (q, J¼323 Hz).
J¼325 Hz). GCeMS m/z 210 (Mþ). The spectroscopic data are con-
GCeMS m/z 260 (Mþ). HRMS (EI) m/z: calcd for [M]þ: C11H7F3O2S:
sistent with those reported in the literature.
260.0119; found: 260.0121. IR (KBr)
1064, 1141, 1124，664, 578 cmꢂ1
n 3057, 2919, 2849, 1624, 1364,
.
4.2.2. 1-Methyl-4-(trifluoromethylsulfonyl)benzene (Table 2, entry
2).7e,21 Obtained as a colorless oil in 70% yield (78.9 mg). Rf (5%
4.2.9. 1-Methoxy-4-(trifluoromethylsulfonyl)benzene7e,24 (Table 2,
entry 9). Obtained as a yellow oil in 41% yield (49.6 mg). Rf (5%
Et2O/pentane): 0.33. 1H NMR (500 MHz, CDCl3):
d
7.94 (d, J¼8.1 Hz,
2H), 7.49 (d, J¼8.1 Hz, 2H), 2.54 (s, 3H). 19F NMR (470 MHz, CDCl3):
Et2O/pentane): 0.19. 1H NMR (500 MHz, CDCl3):
d
7.98 (d, J¼9.0 Hz,
d
ꢂ78.67(s, 3F). 13C NMR (126 MHz, CDCl3):
d
148.4, 130.8, 130.6,
2H), 7.14e7.11 (m, 2H), 3.96 (s, 3H). 19F NMR (470 MHz, CDCl3):
d
128.2, 119.9 (q, J¼323 Hz), 22.0. GCeMS m/z 224 (Mþ). The spec-
ꢂ78.88 (s, 3F). 13C NMR (126 MHz, CDCl3):
d 166.4, 133.2, 122.0,
troscopic data are consistent with those reported in the literature.
119.9 (q, J¼323 Hz), 115.3, 55.7. GCeMS m/z 240 (Mþ). The spec-
troscopic data are consistent with those reported in the literature.
4.2.3. 1-Methyl-2-(trifluoromethylsulfonyl)benzene (Table 2, entry
3).21,22 Obtained as a colorless oil in 76% yield (84.8 mg). Rf (5%
4.2.10. 4-(Trifluoromethylsulfonyl)benzonitrile7c (Table 2, entry
10). Obtained as a white solid in 88% yield (103.6 mg). Rf (10% Et2O/
Et2O/pentane): 0.33. 1H NMR (500 MHz, CDCl3):
d
8.10 (d, J¼8.0 Hz,
1H), 7.73e7.68 (m, 1H), 7.43e7.53 (m, 2H), 2.76 (s, 3H). 19F NMR
pentane): 0.26. 1H NMR (500 MHz, CDCl3):
d
8.21 (d, J¼8.3 Hz, 2H),
(470 MHz, CDCl3):
d
ꢂ78.08 (s, 3F). 13C NMR (126 MHz, CDCl3):
8.02 (d, J¼8.3 Hz, 2H). 19F NMR (470 MHz, CDCl3):
d
ꢂ77.67 (s, 3F).
d
142.2, 136.4, 133.6, 133.4, 129.8, 127.2, 120.1 (q, J¼323 Hz), 20.7.
13C NMR (126 MHz, CDCl3):
d 135.6, 133.5, 131.4, 120.8, 119.3
GCeMS m/z 224 (Mþ). The spectroscopic data are consistent with
(q, J¼323 Hz), 116.4. GCeMS m/z 235 (Mþ).
those reported in the literature.
4.2.11. 1-Nitro-3-(trifluoromethylsulfonyl)benzene25 (Table 2, entry
11). Obtained as a yellow oil in 75% yield (95.6 mg). Rf (10% Et2O/
4.2.4. 1-Isopropyl-4-(trifluoromethylsulfonyl)benzene (Table 2, entry
4). Obtained as a colorless oil in 51% yield (63.6 mg). Rf (5% Et2O/
pentane): 0.13. 1H NMR (500 MHz, CDCl3):
d 8.91 (s, 1H), 8.75e8.72
pentane): 0.36. 1H NMR (500 MHz, CDCl3):
d
7.98 (d, J¼8.4 Hz, 2H),
(m, 1H), 8.41 (d, J¼8.0 Hz, 1H), 7.99 (t, J¼8.0 Hz, 1H). 19F NMR
7.54 (d, J¼8.4 Hz, 2H), 3.13e3.02 (m, 1H), 1.33 (d, J¼6.9 Hz, 6H). 19F
(470 MHz, CDCl3):
d
ꢂ77.53 (s, 3F). 13C NMR (126 MHz, CDCl3):
NMR (470 MHz, CDCl3):
d
ꢂ78.60 (s, 3F). 13C NMR (126 MHz, CDCl3):
d
148.8, 136.0, 133.8, 131.5, 130.9, 126.0, 119.5 (q, J¼323 Hz). GCeMS
d
158.8,131.0,128.6,128.1,119.8 (q, J¼323 Hz), 34.6, 23.5. GCeMS m/
m/z 255 (Mþ). The spectroscopic data are consistent with those
z 252 (Mþ). HRMS (EI) m/z: calcd for [M]þ: C10H11F3O2S: 252.0432;
found: 252.0434. IR (KBr) 2966, 2920, 1595, 1369, 1219, 1196, 1142,
1078 cmꢂ1
reported in the literature.
n
.
4.2.12. 1-Fluoro-4-(trifluoromethylsulfonyl)benzene26 (Table 2, entry
12). Obtained as a yellow oil in 38% yield (43.9 mg). Rf (5% Et2O/
4.2.5. 1-tert-Butyl-4-(trifluoromethylsulfonyl)benzene (Table 2, entry
5). Obtained as a white solid in 71% yield (94.5 mg); mp 61e62 ꢀC.
pentane): 0.52. 1H NMR (500 MHz, CDCl3):
d
8.14e8.09 (m, 2H),
ꢂ78.16 (s, 3F),
167.7 (d, J¼260.3 Hz),
7.42e7.36 (m, 2H). 19F NMR (470 MHz, CDCl3):
d
Rf (5% Et2O/pentane): 0.43. 1H NMR (500 MHz, CDCl3):
d
7.98 (d,
ꢂ97.40 (s, 1F). 13C NMR (126 MHz, CDCl3):
d
J¼8.5 Hz, 2H), 7.70 (d, J¼8.5 Hz, 2H), 1.40 (s, 9H). 19F NMR (470 MHz,
134.0 (d, J¼10.3 Hz), 127.2, 119.7 (q, J¼323 Hz), 117.5 (d, J¼22.7 Hz).
GCeMS m/z 228 (Mþ). The spectroscopic data are consistent with
those reported in the literature.
CDCl3):
d
ꢂ78.57 (s, 3F). 13C NMR (126 MHz, CDCl3):
d 161.1, 130.7,
128.1, 127.0, 119.9 (q, J¼323 Hz), 35.7, 30.9. GCeMS m/z 266 (Mþ).
HRMS (EI) m/z: calcd for [M]þ: C11H13F3O2S: 266.0588; found:
266.0596. IR (KBr)
591 cmꢂ1
n
2965, 2924, 1593, 1362, 1218, 1144, 637,
4.2.13. 8-(Trifluoromethylsulfonyl)quinoline (Table 2, entry 13).
Obtained as a white solid in 81% yield (105.3 mg); mp 106e108 ꢀC.
.
Rf (5% Et2O/pentane): 0.17. 1H NMR (500 MHz, CDCl3):
d 9.21e9.18
4.2.6. 4-(Trifluoromethylsulfonyl)biphenyl (Table 2, entry 6). Obtained
as a white solid in 60% yield (86.1 mg); mp 71e73 ꢀC. Rf (5% Et2O/
(m, 1H), 8.70e8.66 (m, 1H), 8.35 (dd, J¼8.3, 1.5 Hz, 1H), 8.31 (dd,
J¼8.3, 1.5 Hz, 1H), 7.81 (t, J¼7.8 Hz, 1H), 7.66e7.64 (m). 19F NMR
pentane): 0.43. 1H NMR (500 MHz, CDCl3):
d
8.13 (d, J¼8.4 Hz, 2H),
(470 MHz, CDCl3):
d
ꢂ74.35 (s, 3F). 13C NMR (126 MHz, CDCl3):

2632
X. Lin et al. / Tetrahedron 69 (2013) 2628e2632
8. Kolomeitsev, A. A.; Movchun, V. N.; Kondratenko, N. V.; Yagupolski, Y. L. Syn-
d
152.5, 145.1, 137.2, 136.5, 136.1, 130.7, 129.1, 125.7, 123.0, 120.2 (q,
thesis 1990, 1151e1152.
J¼323 Hz). GCeMS m/z 261 (Mþ). Anal. Calcd for C10H6F3NO2S: C,
9. (a) Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470e477; (b) Lundgren,
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45.98; H, 2.32; N, 5.36. Found: C, 45.88; H, 2.60. N, 5.35. IR (KBr)
n
3056, 1610, 1596, 1560, 1495, 1354, 1200, 1106, 833, 790, 673 cmꢂ1
.
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Acknowledgements
We acknowledge the financial support from National Natural
Science Foundation of China (21072030) and Fuzhou University
(022318) to Z.W. and King Abdullah University of Science and
Technology to K.-W.H.
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Supplementary data
Copies of NMR spectra for all products. Supplementary data
related to this article. Supplementary data related to this article can
be found online at http://dx.doi.org/10.1016/j.tet.2013.01.041.
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