Selective Trifluoromethylthiolation and Trifluoromethylsulfinylation of Indoles with Sodium Trifluoromethanesulfinate Promoted by Phosphorus Reagents

Article abstract of DOI:10.1002/ejoc.201700661

Direct trifluoromethylthiolation and trifluoromethylsulfinylation reactions by using sodium trifluoromethanesulfinate were promoted by different phosphorus reagents to selectively occur under mild and transition-metal-free conditions. In the presence of phosphorus trichloride, sodium trifluoromethanesulfinate readily underwent a reaction with indole and its derivatives in N,N-dimethylformamide (DMF) at room temperature to give 3-trifluoromethylthiolated products in good yields. Trifluoromethylsulfinylation reactions, however, occurred at the C-3 position when phosphorus oxychloride was used to give the corresponding sulfoxides in high yields. This protocol was further extended to the use of other sodium perfluoroalkanesulfinates.

Full text of DOI:10.1002/ejoc.201700661

A Journal of
Accepted Article
Title: Selective Trifluoromethylthiolation and Trifluoromethylsulfinylation
of Indoles with Sodium Trifluoromethanesulfinate promoted by
Phosphorus Reagents
Authors: Jin-Tao Liu, Dong-Wei Sun, Xu Jiang, Min Jiang, and Yun Lin
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201700661
Link to VoR: http://dx.doi.org/10.1002/ejoc.201700661
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10.1002/ejoc.201700661
European Journal of Organic Chemistry
FULL PAPER
Selective
Trifluoromethylthiolation
of Indoles
and
Trifluoromethylsulfinylation
with
Sodium
Trifluoromethanesulfinate promoted by Phosphorus Reagents
Dong-Wei Sun,[a] Xu Jiang,[b] Min Jiang,[a] Yun Lin,*[b] and Jin-Tao Liu*[a]
Dedication ((optional))
Abstract:
Direct
trifluoromethylthiolation
and
utilization. Although a series of highly efficient and CF3S-based
[8]
reagents (such as Me4NSCF3,[7] AgSCF3 and CuSCF3 was
trifluoromethylsulfinylation with sodium trifluoromethanesulfinate
promoted by different phosphorus reagent were achieved selectively
under transition metal-free and mild conditions. In the presence of
phosphorus trichloride, sodium trifluoromethanesulfinate reacted
readily with indole and its derivatives in DMF at room temperature to
give 3-trifluoromethylthiolated products in good yields. While
trifluoromethylsulfinylation reaction occured at C-3 position when
phosphorus oxychloride was used, and the corresponding sulfoxides
were obtained in high yields. The protocol could also be expanded to
other sodium perfluoroalkanesulfinates.
discovered in the last decades,[9] these reagents also have some
shortcomings which is that multiple steps are required before its
application, and expensive chemicals could be used. In the past
decade, several mild and efficient CF3S-N or CF3S-O based
electrophilic trifluoromethylthiolating reagents were developed
and
achieved
great
success
reactions.[9]
in
a
range
a
of
new
trifluoromethylthiolation
Recently,
trifluoromethylthiolation strategy emerged involving the
conbination of trifluoromethanesulfonyl chloride (CF3SO2Cl) and
a reducing reagent, such as PMe3,[10] (EtO)2P(O)H,[11] and
CF3SO2Cl/PPh3.[12]
Sodium trifluoromethanesulfinate (CF3SO2Na), also known as
Langlois reagent, and other sodium perfluoroalkanesulfinates
are cheap and easily available commercial chemicals. In 2009,
Magnier and co-workers reported that a small quantity of
trifluoromethylthiolation product was formed in the reaction of
Introduction
In recent years, fluorined compounds have attracted more and
more attention due to their significant application in medicinal
and life sciences.[1] It is well known that the introduction of
fluorine atom or fluorine-containing groups into organic
molecules can improve their physical, chemical and biological
properties.[2] Among various fluorine-containing groups,
CF3SO2K and biphenyl for the
reagent.[13] In 2015, Zhang et al reported a CuCl catalyzed
trifluoromethylthiolation reaction of indoles with
preparation of Umemoto
CF3SO2Na/(EtO)2P(O)H system.[14] And metal-free electrophilic
fluoroalkylthiolation with the similar reagent system was
achieved very recently.[15] Meanwhile, Cai and co-workers
reported a transition metal-free trifluoromethylthiolation reaction
of indole and its derivatives with CF3SO2Na/PPh3 system, and it
was found that an additional X+ source such as N-
chlorophthalimide and N-Bromophthalimide was essential for the
reaction.[16]
trifluoromethylthiol
(CF3S) plays an important role in
organofluorine chemistry because of its electron-withdrawing
effect and high lipophilicity.[3] In addition, enhancement of
biological activity has also been found in some
trifluoromethylsulfinyl-containing compounds such as insecticide
Fipronil and its analogues.[4]
So far, great progress has been made to introduce
trifluoromethylthiol group into aromatic compounds, and a series
On the other hand, trifluoromethylsulfides can be oxidized to
the corresponding trifluoromethyl sulfoxides.[17] Another method
to make trifluoromethylated sulfoxides is nucleophilic
trifluoromethylation of sulfinyl halides or sulfinic esters with
TMSCF3.[18] Direct trifluoromethylsulfinylation of aromatic
compounds with CF3S(O)F and CF3S(O)Cl is rarely reported due
to the instability and toxicity of these reagents.[19] In 2016,
Cahard and co-workers reported the synthesis of hereroaryl
trifluoromethyl sulfoxides by direct trifluoromethylsulfinylation of
hereroarenes with CF3SO2Cl/PCy3 system, but low temperature
(-78℃) was required.[20] http://www.njnu.edu.cn/
Previously, our group had focus on the chemistry of
perfluoroalkanesulfinates and their derivatives.[21] During the
study on the synthesis and properties of perfluoroalkanesulfenyl
chlorides (RfSCl), it was found that RfSCl was good
perfluoroalkylthiolating reagent for some aromatic compounds,
especially indole.[22] Considering that CF3SCl may be formed in
situ by the reduction of CF3SO2Na with a chlorine-containing
phosphorus (III) reagent and the importance of inexpensive and
of
electrophilic
trifluoromethylthiolating
reagents
were
developed.[5] Initially, highly reactive trifluoromethanesulfenyl
chloride (CF3SCl) was used for direct trifluoromethylthiolation,[6]
but its toxicity and hard-to-handle gaseous nature limited its
[a]
[b]
D.-W. Sun, Dr. M. Jiang, Prof. Dr. J.-T. Liu*
Key Laboratory of Organofluorine Chemistry
Shanghai Institute of Organic Chemistry, Chinese Academy of
Science
345 Lingling Road, Shanghai 200032 (China)
E-mail: jtliu@sioc.ac.cn
Homepage: http://liujintao.sioc.ac.cn
X, Jiang, Dr. Y. Lin*
Jiangsu Key Laboratory of Biofunctional Materials
College of Chemistry and Materials Science, Nanjing Normal
University
1 Wenyuan Road, Nanjing 210023 (China)
E-mail: linyun@njnu.edu.cn
Homepage: http://www.njnu.edu.cn/
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201700661
European Journal of Organic Chemistry
FULL PAPER
effective trifluoromethylthiolation method, we further studied the
reactions of indole and its derivatives with CF3SO2Na in the
presence of different phosphorus reagents. The results are
reported in this paper.
(DMF) at room temperature. However, 19F NMR monitoring
showed that the reaction was complicated and no desired
product was isolated after 30min (Table 1, entry 1).
Triphenylphosphine (PPh3) also failed to promote the desired
reaction (entry 2). Gratefully, when phosphorus trichloride (PCl3)
was used as reducing reagent, trifluoromethylthiolation and
trifluoromethylsulfinylation products (2a and 3a) were obtained in
58% and 39% yields, respectively (entry 2). Further investigation
showed that increasing the amount of CF3SO2Na or PCl3 was in
favour of the selectivity of trifluoromethylthiolation product.
Screening the ratio of reactants indicated that 85% yield of 2a
Results and Discussion
In our preliminary experiments, indole (1a) was chosen as the
model substrate and ordinary phosphine reagents were used.
The reaction was carried out with 1.2 equiv of CF3SO2Na and
1.0 equiv of trimethylphosphine (PMe3) in N, N-dimethyl formide
could be achieved with a ratio of indole/CF3SO2Na/PCl3
=
1:1.2:3, and only trace of 3a was observed (entries 4-10).
Various solvents were next examined. It was found that
acetonitrile, tetrahydrofuran (THF), 1,4-dioxane, toluene and
dimethylamide (DMA) could not give better result although they
also afforded 2a as major product, and DMF was the most
suitable solvent for this reaction (entries 11-16). To our surprise,
when phosphorus oxychloride (P(O)Cl3) was used instead of
PCl3, 3a was obtained as major product (entries 17-19). After
condition screening, the optimal conditions for the formation of
3a were set to 1.0 equiv of 1a, 1.2 equiv of CF3SO2Na and 1.0
equiv of P(O)Cl3 in DMF at room temperature (entry 19).
Table 1: Condition optimization for the trifluoromethylthiolation and
trifluoromethylsulfinylation of 1a with CF3SO2Na
entrya [P]
1a:CF3SO2Na:[P] solvent
2a/%b 3a/%b
1
PMe3
PPh3
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:2
1:1.5:1.5
1:1.5:2
1:1.5:3
1:1.2:2
1:1.2:3
1:1.2:4
1:1.2:3
1:1.2:3
1:1.2:3
1:1.2:3
1:1.2:3
1:1.2:3
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
CH3CN
THF
0
0
Table 2. Perfluoroalkylthiolation of 1 in the presence of PCl3
2
0
0
c
3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
PCl3
58
69
69
77
71
75
85
73
76
80
39
c
c
c
c
c
c
c
c
c
c
c
c
c
4
trace
4.8
5
6
trace
trace
21
7
8
9
trace
trace
trace
trace
Trace
20
10
11
12
13
14
15
16
17
18
19
1.4-Dioxane 67
Toluene
DMSO
DMA
DMF
60
NR
79
NR
20
P(O)Cl3 1:1.2:1.5
P(O)Cl3 1:1.5:1
P(O)Cl3 1:1.2:1
16
66
DMF
18
62
DMF
trace
89
a Reaction conditions: 1a (0.4 mmol), CH3SO2Na (1.2-1.5 equiv), [P] (1.0-4.0
equiv), solvent (1.0 mL), under N2 at room temperature for 0.5 h. b Determined
C
by 19F NMR using PhCF3 as internal standard. A solution of phosphorus
chloride in dichloromethane (2 M).
a Reaction conditions: 1 (0.4 mmol), RfSO2Na (0.48 mmol), PCl3 (1.2 mmol),
DMF (1 mL) under N2 at room temperature, isolated yields.
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10.1002/ejoc.201700661
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Under the optimized conditions, the scope of substrates was
investigated for the PCl3-promoted reaction. As shown in Table 2,
a series of indoles with both electron-withdrawing and electron-
donating groups at 5, 6 and 7-position (1a-1h) were good
substrate for this trifluoromethylthiolation reaction, affording the
corresponding trifluoromethylthiolated products (2a-2h) in
moderate to good yields (57 to 83%). Usually, the substrate with
an electron-donating substituent gave higher yields. Under
similar conditions, 2-methyl, 2-phenyl and N-methyl indoles
could also react with CF3SO2Na to give the desired products in
good yields and excellent selectivities (2i-2l). Moreover, the
reaction of N-phenyl pyrrole worked well and gave the
corresponding 2-trifluoromethylthiolated product 2m in 80% yield.
When unprotected pyrrole was used as substrate, unexpected
product 2n containing an aldehyde group was obtained in 84%
yield. Except CF3SO2Na, we also tried other sodium
perfluoroalkanesulfinates. It was found that ClCF2CF2SO2Na and
n-C6F13SO2Na could react smoothly with indole in a similar way
to give the corresponding perfluoroalkylthiolation products, but
the yield was lower. Unfortunately, perfluorobutylthiolation was
2-methyl, 2-phenyl and N-methyl indoles were used.
Furthermore, similar transformation was achieved with other
sodium perfluoroalkanesulfinates, such as ClCF2CF2SO2Na, n-
C4F9SO2Na and n-C6F13SO2Na, and the corresponding 3-
perfluoroalkylsulfinylated products 3k-3m were obtained in good
yields.
unsuccessful
under
similar
conditions
and
3-
perfluorobutylsulfinylindole was formed as the major product.
Figure 1. 19F NMR spectra for the mechanistic.
In order to gain insight to the reaction mechanism, we carried
out the following reaction: A mixture of CF3SO2Na (1.5 equiv)
and PCl3 (1.0 equiv) in DMF was stirred at room temperature.
After 10 min, 1.0 equiv of 1a was added. As shown in Figure 1,
19F NMR analysis showed both CF3SCl ( = -45.92 ppm) and
CF3SOCl ( = -75.98 ppm) existed in the reaction system (Figure
1-1). Similarly, the signals of CF3SCl and CF3SOCl were also
observed in the mixture of CF3SO2Na and P(O)Cl3 with a ratio
of 1.2:1 in DMF (Figure 1-2). After addition of 1a to the P(O)Cl3-
promoted reaction system, 2a and 3a were rapidly produced
(Figure 1-3).
Table 3. Perfluoroalkylsulfinylation of 1 in the presence of P(O)Cl3
Further investigation found that 2a and 3a could not transfer
each other under the two standard conditions. It can be inferred
that the formation of 2a and 3a was a competitive process.
Based on the above experimental results and previous
reports,[11-15, 22] it could be deduced that CF3SCl and CF3SOCl
were formed as key intermediates in the reaction system and
underwent the subsequent trifluoromethylthiolation and
trifluoromethylsulfinylation reaction with 1, respectively. In the
PCl3-promoted reaction, increasing the amount of CF3SO2Na or
PCl3 was favor for the formation of CF3SCl and thus resulted in
better selectivity for product 2. On the contrary, in the P(O)Cl3-
promoted reaction, decreasing the equivalent of CF3SO2Na and
P(O)Cl3 easily afforded 3 with high yield and good selectivity.
Reaction conditions: 1 (0.4 mmol), RfSO2Na (0.48 mmol), P(O)Cl3 (0.4 mmol),
DMF (1 mL) under N2 at room temperature, isolated yields.
Indoles 1 were also examined in the P(O)Cl3-promoted
trifluoromethylsulfinylation reaction and the results are
summarized in Table 3. As expected, the reaction showed a
wide scope for the structural variation of 1 and excellent
selectivity was achieved with compound 3 as major product in
each reaction. High yields were obtained not only with electron-
donating substituted products, but also with electron-withdrawing
substituted compounds. Good results were also obtained when
Conclusions
In summary, we have developed an efficient protocol for the
direct trifluoromethylthiolation and trifluoromethylsulfinylation of
indole and its derivatives with sodium trifluoromethanesulfinate.
By using different phosphorus reagent, trifluoromethylthiolation
and trifluoromethylsulfinylation products could be obtained
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10.1002/ejoc.201700661
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CDCl3) δ 8.45 (br, 1H), 7.51 (s, 1H), 7.32 (d, J = 8.9 Hz, 1H), 7.22 (s, 1H),
6.95 (q, J = 8.9 Hz, 1H), 3.90 (s, 3H). 19F NMR (376 MHz, CDCl3) δ -
44.71 (s).
selectively in good yields, respectivity. The reaction tolerates a
wide range of functional groups, providing a practical method for
the
synthesis
of
various
trifluoromethylthiol-
compounds. The
and
key
trifluoromethylsulfinyl-containing
7-Methoxy-3-( trifluorooctyl)thio)-1H-indole (2d): Yellow solid, 82.1 mg,
yield: 83%. m.p. 85-87 ℃. 1H NMR (400 MHz, CDCl3) δ 8.73 (br, 1H),
7.49 (d, J = 2.7 Hz, 1H), 7.37 (d, J = 8.0 Hz, 1H), 7.17 (t, J = 7.9 Hz, 1H),
6.71 (d, J = 7.7 Hz, 1H), 3.95 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
146.25 (s), 132.20 (s), 130.84 (s), 129.44 (q, J = 317.0 Hz), 126.70 (s),
122.10 (s), 111.76 (s), 103.03 (s), 95.82 (s), 55.47 (s). 19F NMR (376
MHz, CDCl3) δ -44.72 (s). ESI-MS (m/z, %): 248.0 (100) [M+H]+. HRMS
(ESI) Calcd. for C10H9F3NOS [M+H]+ requires 248.0351, found 248.0349.
advantage of this method includes: cheap and easily available
reagents, easy-to-handle, transition-metal-free and mild reaction
conditions. Moreover, the protocol could also be expanded to
perfluoromethylthiolation
and
perfluoromethylsulfinylation
reaction with sodium perfluoroalkanesulfinates.
Experimental Section
5-Chloro-3-((trifluoromethyl)thio)-1H-indole (2e): Yellow solid, 39.2 mg,
yield: 75%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ
8.55 (br, 1H), 7.75 (d, J = 1.2 Hz, 1H), 7.55 (d, J = 2.8 Hz, 1H), 7.34 (d, J
= 8.8 Hz, 1H), 7.25 – 7.21 (m, 1H). 19F NMR (376 MHz, CDCl3) δ -44.56
(s).
General information
Unless otherwise mentioned, solvents and reagents were purchased
from commercial sources and used as received. Solvents were freshly
distilled by standard procedure prior to use. Melting points were
measured on a RY-I apparatus and uncorrected. 1H NMR and 19F NMR
were recorded on 1H at 400 Hz and 19F at 376 MHz, respectively. 13C
NMR spectra were recorded on 13C at 100 MHz. High Resolution Mass
Spectra (HRMS) were recorded on an IonSpec FT-ICR mass
spectrometer with ESI resource.
6-Chloro-3-((trifluoromethyl)thio)-1H-indole (2f): Yellow solid, 70.5 mg,
yield: 70%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ
8.55 (br, 1H), 7.71 (d, J = 8.5 Hz, 1H), 7.54 (d, J = 2.7 Hz, 1H), 7.43 (d, J
= 1.7 Hz, 1H), 7.25 (q, J = 4.0 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ -
44.54 (s).
Typical procedure for the trifluoromethylthiolation
To a solution of indole 1a (0.4 mmol) and CF3SO2Na (0.48 mmol) in DMF
(1.0 mL) was added a solution of phosphorus chloride (1.2 mmol in
dichloromethane, 2 M) dropwise over a period of 3 min. The mixture was
stirred at room temperature for 0.5h. After the reaction was completed
(monitored by 19F NMR), the mixture was quenched with water. The
aqueous layer was extracted with EtOAc three times. The organic layers
were combined, dried over Na2SO4 and concentrated. The resulting
crude product was purified by column chromatography on silica gel
(petroleum ether/ethyl acetate=10/1 v/v) to give the corresponding
product 2a.
5-Nitro-3-((trifluoromethyl)thio)-1H-indole (2g): Yellow solid, 71.3 mg,
yield: 68%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ
8.96 (br, 1H), 8.74 (s, 1H), 8.21 (d, J = 8.9 Hz, 1H), 7.73 (s, 1H), 7.51 (d,
J = 9.4 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ -44.22 (s).
3-((Trifluoromethyl)thio)-1H-indole-5-carbaldehyde (2h): Yellow solid,
55.9 mg, yield: 57%. m.p. 148-150 ℃. 1H NMR (400 MHz, CDCl3) δ 10.10
(s, 1H), 8.96 (br, 1H), 8.32 (s, 1H), 7.88 (q, J = 8.5 Hz, 1H), 7.67 (d, J =
2.0 Hz, 1H), 7.54 (d, J = 8.5 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ
192.35 (s), 139.55 (s), 134.57 (s), 131.22 (s), 129.90 (s), 128.98 (q, J =
308.2 Hz), 124.76 (s), 123.33 (s), 112.61 (s), 97.92 (s). 19F NMR (376
MHz, CDCl3) δ -44.30 (s). ESI-MS (m/z, %): 246.0 (100) [M+H]+. HRMS
(ESI) Calcd. for C10H7F3NOS [M+H]+ requires 246.0195, found 246.0192.
Typical procedure for the trifluoromethylsulfinylation
To a solution of indole 1a (0.4 mmol) and CF3SO2Na (0.48 mmol) in DMF
(1.0 mL) was added P(O)Cl3 (0.4 mmol). The mixture was stirred at room
temperature for 0.5h. After the reaction was completed (monitored by 19
F
2,5-Dimethyl-3-((trifluoromethyl)thio)-1H-indole (2i): Yellow solid, 77.5
mg, yield: 79%. This is a known compound.[24] 1H NMR (400 MHz,
CDCl3) δ 8.21 (br, 1H), 7.47 (s, 1H), 7.19 (d, J = 8.2 Hz, 1H), 7.02 (d, J =
8.0 Hz, 1H), 2.54 (s, 3H), 2.46 (s, 3H). 19F NMR (376 MHz, CDCl3) δ -
44.54 (s).
NMR), the mixture was quenched with water. The aqueous layer was
extracted with EtOAc three times and the organic layers were combined,
dried over Na2SO4 and concentrated. The resulting crude product was
purified by column chromatography on silica gel (petroleum ether/ethyl
acetate=5/1 v/v) to give the corresponding product 3a.
3-((Trifluoromethyl)thio)-2-methyl-1H-indole (2j): Brown solid, 61.0 mg,
yield: 66%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ
8.30 (br, 1H), 7.76 – 7.61 (m, 1H), 7.35 – 7.26 (m, 1H), 7.24 – 7.16 (m,
2H), 2.57 (s, 3H). 19F NMR (376 MHz, CDCl3) δ -44.49 (s).
3-((Trifluoromethyl)thio)-1H-indole (2a): Yellow solid, 68.6 mg, yield:
79%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ 8.52 (br,
1H), 7.81 (d, J = 7.6 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 7.44 – 7.42 (m,
1H), 7.32 – 7.28 (m, 2H). 19F NMR (376 MHz, CDCl3) δ -44.63 (s).
2-Phenyl-3-((trifluoromethyl)thio)-1H-indole (2k): Yellow solid, 91.5
mg, yield: 78%. This is a known compound.[14] 1H NMR (400 MHz,
CDCl3) δ 8.59 (br, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 7.2 Hz, 2H),
7.58 – 7.45 (m, 3H), 7.45 – 7.39 (m, 1H), 7.28-7.30 (m, 2H). 19F NMR
(376 MHz, CDCl3) δ -43.49 (s).
5-Methyl-3-((trifluoromethyl)thio)-1H-indole (2b): Brown solid, 75.8 mg,
yield: 82%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ
8.39 (br, 1H), 7.55 (s, 1H), 7.46 (d, J = 2.5 Hz, 1H), 7.28 (d, J = 8.4 Hz,
1H), 7.08 (d, J = 8.3 Hz, 1H), 2.46 (s, 3H). 19F NMR (376 MHz, CDCl3) δ -
44.69 (s).
3-((Trifluoromethyl)thio)-1-methyl-1H-indole (2l): Yellow solid, 63.8
mg, yield: 69%. This is a known compound.[14] 1H NMR (400 MHz,
CDCl3) δ 7.79 (d, J = 7.6 Hz, 1H), 7.41 – 7.34 (m, 2H), 7.33 – 7.28 (m,
3-((Trifluoromethyl)thio)-5-methoxy-1H-indole (2c): Yellow solid, 80.1
mg, yield: 81%. This is a known compound.[14] 1H NMR (400 MHz,
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10.1002/ejoc.201700661
European Journal of Organic Chemistry
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1H), 7.28 – 7.27 (m, 1H), 3.85 (s, 3H). 19F NMR (376 MHz, CDCl3) δ -
[M+H]+. HRMS (ESI) Calcd. for C10H9F3NO2S [M+H]+ requires 264.0301,
found 264.0297.
45.00 (s).
1-phenyl-2-((trifluoromethyl)thio)-1H-pyrrole (2m): Yellow oil, 77.84
[23]
mg, yield: 80%. This is a known compound.
1H NMR (400 MHz,
5-Chloro-3-((trifluoromethyl)sulfinyl)-1H-indole (3e): Yellow solid,
93.1 mg, yield: 87%. m.p. 133-135 ℃. 1H NMR (400 MHz, DMSO) δ
12.61 (br, 1H), 8.40 (s, 1H), 7.76 (s, 1H), 7.59 (d, J = 8.7 Hz, 1H), 7.32 (d,
J = 8.6 Hz, 1H). 13C NMR (101 MHz, DMSO) δ 136.06 (s), 135.52 (s),
126.95 (s), 126.21 (q, J = 337.8 Hz), 125.41 (s), 124.31 (s), 119.24 (s),
115.37 (s), 106.43 (s). 19F NMR (376 MHz, DMSO) δ -73.02 (s). ESI-MS
(m/z, %): 268.0 (100) [M+H]+. HRMS (ESI) Calcd. for C9H6ClF3NOS
[M+H]+ requires 267.9805 , found 267.9803.
CDCl3) δ 7.45 (t, J = 7.7 Hz, 2H), 7.38 – 7.36 (m, 2H), 7.33 – 7.29 (m,
2H), 7.08 (t, J = 2.4 Hz, 1H), 6.50 (s, 1H). 19F NMR (376 MHz, CDCl3) δ -
45.19 (s).
5-((Trifluoromethyl)thio)-1H-pyrrole-2-carbaldehyde (2n): Yellow solid,
1
66.6 mg, yield: 84%. m.p. 49-50 ℃. H NMR (400 MHz, DMSO) δ 13.15
(br, 1H), 9.56 (s, 1H), 7.07-7.06 (m, 1H), 6.75-6.73 (m, 1H). 13C NMR
(100 MHz, DMSO) δ 180.95, 137.31, 128.76 (q, J = 308.04 Hz), 122.06,
120.32, 116.19. 19F NMR (376 MHz, DMSO) δ -43.02 (s). HRMS (ESI)
Calcd. for C6H5F3NOS [M+H]+ requires 196.0038, found 196.0037.
3-((trifluoromethyl)sulfinyl)-1H-indole-5-carbaldehyde (3f): Yellow
solid, 83.6 mg, yield: 80%. m.p. 155-156 ℃. 1H NMR (400 MHz, DMSO) δ
12.84 (br, 1H), 10.04 (s, 1H), 8.51 (s, 1H), 8.40 (s, 1H), 7.83 – 7.81 (m,
1H), 7.73 (d, J = 8.5 Hz, 1H). 13C NMR (101 MHz, DMSO) δ 193.22 (s),
140.93 (s), 136.33 (s), 131.41 (s), 125.49 (q, J = 334.8 Hz), 124.51 (s),
124.24 (s), 124.04 (s), 114.46 (s), 108.63 (s). 19F NMR (376 MHz,
DMSO) δ -72.87 (s). ESI-MS (m/z, %): 262.0 (100) [M+H]+. HRMS (ESI)
Calcd. for C10H7F13NOS [M+H]+ requires 262.0144, found 262.0142.
3-((2-Chloro-1,1,2,2-tetrafluoroethyl)thio)-1H-indole (2o): Yellow solid,
46.5 mg, yield: 41%. m.p. 46-47 ℃. 1H NMR (400 MHz, CDCl3) δ 8.51 (br,
1H), 7.80 (d, J = 8.2 Hz, 1H), 7.52 (d, J = 2.6 Hz, 1H), 7.42 – 7.40 (m,
1H), 7.31 – 7.26 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 136.03 (s),
133.46 (s), 129.92 (s), 123.41 (s), 121.66 (s), 119.47 (s), 111.73 (s),
94.23 (s). 19F NMR (376 MHz, CDCl3) δ -67.62 (t, J = 6.3 Hz, 2F), -88.47
(t, J = 6.3 Hz, 2F). ESI-MS (m/z, %): 282.0 (100) [M]. HRMS (ESI) Calcd.
For C10H6ClF4NS [M]+ requires 282.9840, found 282.9837.
2,5-Dimethyl-3-((trifluoromethyl)sulfinyl)-1H-indole (3g): Yellow solid,
95.0 mg, yield: 91%. m.p. 198-199℃. 1H NMR (400 MHz, DMSO) δ 12.19
(br, 1H), 7.51 (s, 1H), 7.31 (d, J = 8.3 Hz, 1H), 7.02 (d, J = 8.2 Hz, 1H),
2.51 (s, 3H), 2.34 (s, 3H). 13C NMR (101 MHz, DMSO) δ 145.11 (s),
134.48 (s), 130.91 (s), 126.67 (q, J = 338.4 Hz), 125.68 (s), 124.79 (s),
119.32 (s), 112.21 (s), 102.02 (s), 21.65 (s), 12.27 (s). 19F NMR (376
MHz, DMSO) δ -72.34 (s). ESI-MS (m/z, %): 262.0 (100) [M+H]+. HRMS
(ESI) Calcd. for C11H11F3NOS [M+H]+ requires 262.0508, found 262.0505.
3-((Perfluorohexyl)thio)-1H-indole (2q): White solid, 50.5 mg, yield:
27%. This is a known compound.[14] 1H NMR (400 MHz, CDCl3) δ 8.55 (br,
1H), 7.78 (d, J = 8.2 Hz, 1H), 7.54 (d, J = 2.3 Hz, 1H), 7.42 (d, J = 6.6 Hz,
1H), 7.31 – 7.27 (m, 2H). 19F NMR (376 MHz, CDCl3) δ -80.82 (t, J = 10.0
Hz, 3F), -88.17 (tt, J = 11.28, 1.13 Hz, 2F), -119.44 (t, J = 3.78 Hz, 2F), -
121.46 – -121.47 (m, 2F), -122.83 – -122.84 (m, 2F), -126.60 – -133.04
(m, 2F).
2-Methyl-3-((trifluoromethyl)sulfinyl)-1H-indole (3h): Yellow solid,
86.0 mg, yield: 87%. This is a known compound.[20] 1H NMR (400 MHz,
CDCl3) δ 8.90 (br, 1H), 7.94 (d, J = 7.3 Hz, 1H), 7.34 (d, J = 7.4 Hz, 1H),
7.26 (s, 1H), 7.24 – 7.16 (m, 1H). 19F NMR (376 MHz, CDCl3) δ -72.32
(s).
3-((Trifluoromethyl)sulfinyl)-1H-indole (3a): Yellow solid, 77.4 mg,
yield: 83%. This is a known compound.[20] 1H NMR (400 MHz, CDCl3) δ
9.31 (br, 1H), 7.94 (d, J = 7.9 Hz, 1H), 7.75 (d, J = 2.8 Hz, 1H), 7.46 (d, J
= 8.0 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 7.27 – 7.25 (m, 1H). 19F NMR (376
MHz, CDCl3) δ -73.16 (s).
2-Phenyl-3-((trifluoromethyl)sulfinyl)-1H-indole (3i): Yellow solid, 77.9
mg, yield: 63%. m.p. 126-127 ℃. 1H NMR (400 MHz, DMSO) δ 12.79 (br,
1H), 7.91 (d, J = 8.1 Hz, 1H), 7.57-7.55 (m, 6H), 7.32 (t, J = 7.6 Hz, 1H),
7.24 (t, J = 7.6 Hz, 1H). 13C NMR (101 MHz, DMSO) δ 146.41 (s), 136.89
(s), 130.72 (s), 129.84 (s), 129.57 (s), 129.21 (s), 126.90 (q, J = 340.2
Hz), 125.60 (s), 124.46 (s), 122.56 (s), 120.89 (s), 113.25 (s), 103.57 (s).
19F NMR (376 MHz, DMSO) δ -70.77 (s). ESI-MS (m/z, %): 310.0 (100)
[M+H]+. HRMS (ESI) Calcd. for C15H11F3NOS [M+H]+ requires 310.0508,
found 310.0505.
5-Methyl-3-((trifluoromethyl)sulfinyl)-1H-indole (3b): Yellow solid,
81.1 mg, yield: 81%. m.p. 126-127 ℃. 1H NMR (400 MHz, CDCl3) δ 9.20
(br, 1H), 7.73 (s, 1H), 7.69 (d, J = 2.9 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H),
7.15 (d, J = 8.4 Hz, 1H), 2.44 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
135.13 (s), 132.49 (s), 130.99 (s), 126.20 (s), 125.62 (q, J = 335.5 Hz),
124.16 (s), 119.75 (s), 112.22 (s), 107.42 (s), 21.48 (s).19F NMR (376
MHz, CDCl3) δ -73.07 (s). ESI-MS (m/z, %): 248.0 (100) [M+H]+. HRMS
(ESI) Calcd. for C10H9F3NOS [M+H]+ requires 248.0351, found 248.0350.
1-Methyl-3-((trifluoromethyl)sulfinyl)-1H-indole (3j): Yellow solid, 79.1
mg, yield: 80%. This is a known compound.[20] 1H NMR (400 MHz,
CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.67 (s, 1H), 7.45 – 7.34 (m, 2H), 7.30
(t, J = 7.2 Hz, 1H), 3.88 (s, 3H). 19F NMR (376 MHz, CDCl3) δ -73.64 (s).
5-Methoxy-3-((trifluoromethyl)sulfinyl)-1H-indole (3c): Yellow solid,
99.0 mg, yield: 94%. This is a known compound.[20] 1H NMR (400 MHz,
CDCl3) δ 9.04 (br, 1H), 7.71 (s, 1H), 7.35 (d, J = 9.2 Hz, 2H), 6.97 (dd, J
= 8.9 Hz, 1H), 3.83 (s, 3H).19F NMR (376 MHz, CDCl3) δ -73.02 (s).
3-((2-Chloro-1,1,2,2-tetrafluoroethyl)sulfinyl)-1H-indole (3k): Yellow
solid, 92.3 mg, yield: 77%. m.p. 125-127 ℃. 1H NMR (400 MHz, DMSO) δ
12.45 (br, 1H), 8.33 (d, J = 2.4 Hz, 1H), 7.80 (d, J = 7.8 Hz, 1H), 7.55 (d,
J = 8.2 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.21 (t, J = 7.6 Hz, 1H).13C NMR
(101 MHz, DMSO) δ 137.56 (s), 134.30 (s), 124.77 (s), 124.13 (s),
122.41 (s), 120.37 (s), 113.59 (s), 106.66 (s). 19F NMR (376 MHz,
DMSO) δ -67.01 – -67.02 (m, 2F), -109.77 (dt, J = 233.12, 3.76Hz, 1F), -
118.41(d, J = 233.14Hz, 1F). ESI-MS (m/z, %): 300.0 (100) [M+H]+.
7-Methoxy-3-((trifluoromethyl)sulfinyl)-1H-indole (3d): Yellow solid,
94.8 mg, yield: 92%. m.p. 160-162 ℃. 1H NMR (400 MHz, DMSO) δ
12.64 (br, 1H), 8.22 (d, J = 3.2 Hz, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.13 (t, J
= 8.0 Hz, 1H), 6.85 (d, J = 7.8 Hz, 1H), 3.92 (s, 3H). 13C NMR (101 MHz,
DMSO) δ 147.17 (s), 133.60 (s), 127.74 (s), 126.12 (q, J = 341.5 Hz),
125.81 (s), 123.31 (s), 112.59 (s), 107.37 (s), 104.54 (s), 55.93 (s). 19
NMR (376 MHz, DMSO) δ -72.69 (s). ESI-MS (m/z, %): 264.0 (100)
F
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10.1002/ejoc.201700661
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HRMS (ESI) Calcd. for C10H7ClF4NOS [M+H]+ requires 299.9868, found
299.9864.
Durst, Phosphorus, Sulfur Silicon Relat. Elem. 2002, 177, 1021–
1031; (c) S. Munavalli, D. K. Rohrbaugh, G. W. Wagner, H. D.
Durst, F. R. Longo, Phosphorus, Sulfur Silicon Relat. Elem. 2004,
179, 1635–1643; (d) S. Munavalli, D. K. Rohrbaugh, L. L.
Szafraniec and H. D. Durst, Phosphorus, Sulfur Silicon Relat. Elem.
2006, 181, 305–324.
3-((Perfluorobutyl)sulfinyl)-1H-indole (3l): Yellow solid, 124.2 mg,
yield: 81%. m.p. 127-129 ℃. 1H NMR (400 MHz, DMSO) δ 12.50 (br, 1H),
8.36 (d, J = 2.6 Hz, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H),
7.29 (t, J = 7.6 Hz, 1H), 7.21 (t, J = 7.5 Hz, 1H). 13C NMR (101 MHz,
DMSO) δ 137.60 (s), 134.59 (s), 124.81 (s), 124.18 (s), 122.50 (s),
120.31 (s), 113.62 (s), 106.12 (s). 19F NMR (376 MHz, DMSO) δ -80.44 (t,
J = 9.3 Hz, 3F), -110.73 – -111.39 (m, 1F), -120.07 – -122.54 (m, 3F), -
125.88 – -125.96 (m, 2F). ESI-MS (m/z, %): 384.0 (100) [M+H]+. HRMS
(ESI) Calcd. for C12H7F9NOS [M+H]+ requires 384.0099, found 384.0096.
[7] For selected examples: (a) V. V. Orda, L. M. Yagupolskii, V. F.
Bystrov, A. U. Stepanyants, J. Gen. Chem. 1965, 35, 1628–1636;
(b) S. T. Tavener, D. J. Adams, J. H. Clark, J. Fluorine Chem. 1999,
95, 171–176; (c) D. J. Adams, J. H. Clark, J. Org. Chem. 2000, 65,
1456–1460.
[8] Selective examples: (a) D. J. Adams, A. Goddard, J. H. Clark, D. J.
Macquarrie, Chem. Commun. 2000, 987–988; b) Q. Lefebvre, E.
Fava, P. Nikolaienko, M. Rueping, Chem. Commun. 2014, 50, 6617–
6619; c) P. Nikolaienko, R. Pluta, M. Rueping, Chem. Eur. J. 2014,
20, 9867–9870; d) Y. Huang, X. He, H. Li, Z. Weng, Eur. J. Org.
Chem. 2014, 7324–7328; e) X. Wang, Y. Zhou, G. Ji, G. Wu, M. Li, Y.
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X.-H. Xu, F. L. Qing, Eur. J. Org. Chem. 2014, 4453–4456; g) W. Yin,
Z. Wang, Y. Huang, Adv. Synth. Catal. 2014, 356, 2998–3006; h) K.
Zhang, J. B. Liu, F. L. Qing, Chem. Commun. 2014, 50, 14157–
14160.
3-((Perfluorohexyl)sulfinyl)-1H-indole (3m): White solid, 150.8 mg,
yield: 78%. m.p. 130-131 ℃. 1H NMR (400 MHz, DMSO) δ 12.49 (br, 1H),
8.36 (s, 1H), 7.81 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 8.1 Hz, 1H), 7.29 (t, J =
7.4 Hz, 1H), 7.21 (t, J = 7.4 Hz, 1H). 13C NMR (101 MHz, DMSO) δ
137.61 (s), 134.36 (s), 124.82 (s), 124.07 (s), 122.31 (s), 120.26 (s),
113.54 (s), 106.28 (s). 19F NMR (376 MHz, DMSO) δ -80.78 (t, J = 9.9 Hz,
3F), -110.45 – 111.09 (m, 1F), -119.04 – -121.54 (m, 3F), -121.93 – -
121.98 (m, 2F), -122.78 – -122.85 (m, 2F), -125.75 – -126.51 (m, 2F).
ESI-MS (m/z, %): 484.0 (100) [M+H]+. HRMS (ESI) Calcd. for
C14H7F13NOS [M+H]+ requires 484.0035, , found 484.0028.
[9] Selective examples: (a) A. Ferry, T. Billard, B. R. Langlois, E. Bacqu,
Angew. Chem. Int. Ed. 2009, 48, 8551–8555; Angew. Chem. 2009,
121, 8703–8707. (b) S. Munavalli, D. K. Rohrbaugh, D. I. Rossman,
F. J. Berg, G. W. Wagner, H. D. Durst, Synth. Commun. 2000, 30,
2847–2854; (c) F. Baert, J. Colomb, T. Billard, Angew. Chem. Int.
Ed. 2012, 51, 10382–10385; Angew. Chem. 2012, 124, 10528–
10531; (d) T. Bootwicha, X. Liu, R. Pluta, I. Atodiresei, M. Rueping,
Angew. Chem., Int. Ed. 2013, 52, 12856–12859; (f) M. Rueping, X.
Liu, T. Bootwicha, R. Pluta, C. Merkens, Chem. Commun. 2014, 50,
2508–2511; (g) Q. Xiao, Q. He, J. Li and J. Wang, Org. Lett. 2015,
17, 6090–6093; (h) C. Xu, B. Ma, Q. Shen, Angew. Chem. Int. Ed.
2014, 53, 9316–9320; Angew. Chem. 2014, 126, 9470–9474; (i) H.
Chachignon, D. Cahard, Chinese. J. Chem. 2016, 34, 445–454.
Acknowledgements ((optional))
We thank the National Natural Science Foundation (Nos.
21572257 and 21502213) and Shanghai Sailing Program (No.
15YF1414800) for financial support.
[10] H. Chachignon, M. Maeno, H. Kondo, N. Shibata, D. Cahard, Org.
Lett. 2016, 18, 2467–2470.
Keywords: trifluoromethylthiolation, trifluoromethylsulfinylation,
[11] L. Jiang, W. Yi, Q. Liu, Adv. Synth. Catal. 2016, 358, 3700–3705.
indole, phosphorus trichloride, phosphorus oxychloride
[12] K. Lu, Z. Deng, M. Li, T. Li, X. Zhao, Org. Biomol. Chem. 2017, 15,
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Entry for the Table of Contents (Please choose one layout)
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Key Topic*
Dong-Wei Sun, Xu Jiang, Min Jiang, Yun
Lin* and Jin-Tao Liu*
Page No. – Page No.
Selective
and Trifluoromethylsulfinylation of
Indoles with Sodium
Trifluoromethylthiolation
A Facile method for the selective trifluoromethylthiolation and trifluoromethylsulfinylation of
indoles with CF3SO2Na was developed.
A
series of trifluoromethylthiol and
Trifluoromethanesulfinate promoted
by Phosphorus Reagents
trifluoromethylsulfinyl-containing compounds were synthesized in good yields under mild
and transition-metal-free conditions.
Trifluoromethylthiolation, Trifluoromethylsulfinylation
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