Ruthenium-catalyzed regioselective allylic trifluoromethylthiolation reaction

Article abstract of DOI:10.1021/jo5019393

An efficient Ru-catalyzed regioselective allylic trifluoromethylthiolation reaction of allylic carbonates was developed. The linear allylic trifluoromethyl thioethers were obtained in 52-91% yields. Mechanistic investigation revealed that this reaction proceeds via a double allylic trifluoromethylthiolation sequence.

Full text of DOI:10.1021/jo5019393

Article
pubs.acs.org/joc
Ruthenium-Catalyzed Regioselective Allylic
Trifluoromethylthiolation Reaction
Ke-Yin Ye, Xiao Zhang, Li-Xin Dai, and Shu-Li You*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345
Lingling Lu, Shanghai 200032, China
S
* Supporting Information
ABSTRACT: An efficient Ru-catalyzed regioselective allylic
trifluoromethylthiolation reaction of allylic carbonates was
developed. The linear allylic trifluoromethyl thioethers were
obtained in 52−91% yields. Mechanistic investigation revealed
that this reaction proceeds via a double allylic trifluoromethyl-
thiolation sequence.
allylic halides with stoichiometric amounts of Cu−SCF3
complexes ligated by a bpy9 or a phosphine10 ligand. As part
of our ongoing program toward transition-metal-catalyzed
allylic substitution reactions,11 we envisaged that an appropriate
nucleophilic SCF3 reagent could be utilized in the direct
introduction of a SCF3 unit in a catalytic manner. Herein, we
report the first ruthenium-catalyzed highly regioselective allylic
trifluoromethylthiolation reaction. The current method features
high yields, excellent linear regioselectivity, broad substrate
scope, and an extremely simple operation. Moreover,
mechanistic investigations suggest that a double allylic
trifluoromethylthiolation results in the linear selectivity.
INTRODUCTION
■
Compounds containing a trifluoromethylthio moiety (−SCF3)
are widely spread in many pharmaceuticals and agrochemicals
and thus have fascinated synthetic chemists for a long time
(Figure 1).1,2 Therefore, a large number of procedures to
Figure 1. Examples of SCF3-containing pharmacologically active
compounds.
RESULTS AND DISCUSSION
■
Ru-Catalyzed Allylic Trifluoromethylthiolation Reac-
tion. We began our studies on the direct allylic trifluoro-
methylthiolation reaction by utilizing CsSCF3 (1a)12 as the
nucleophilic trifluoromethylthiolation reagent. The results are
summarized in Table 1. No detectable amount of the desired
trifluoromethyl thioether can be observed with 5 mol % of
Pd(PPh3)4 as the catalyst (entry 1, Table 1). We then turned
our attention to the ruthenium catalysts.13,14 In the presence of
1 mol % of catalyst [Ru]-1,15 the reaction of cinnamyl methyl
carbonate (2a) in MeCN at 50 °C in 12 h afforded (E)-
cinnamyl(trifluoromethyl)sulfane (4a) in 17% yield (entry 2,
Table 1). This reaction is highly regioselective as only a
thermodynamically more stable E-isomer 4a was formed
exclusively. Examination of various linear allyl precursors
revealed that allylic phosphate was the most reactive one,
resulting in the isolation of 4a in 68% yield (entries 2−4, Table
introduce the SCF3 group into organic structures have been
documented.3 These methods generally involve halogen−
fluorine exchange reactions4 or the trifluoromethylation of
sulfur-containing compounds.5 Recently, various new methods
for direct introduction of the SCF3 group have been
described.6,7 However, most of these reported methods employ
stoichiometric amounts of SCF3 sources such as AgSCF3 and
CuSCF3, which are rather expensive. Therefore, an efficient and
direct introduction of a SCF3 unit with a readily available
trifluoromethylthiolation reagent under mild conditions with a
simple operation is highly desirable.
As one of the most powerful tools for constructing carbon−
carbon and carbon−heteroatom bonds, the transition-metal-
catalyzed allylic substitution reaction8 would be a very
straightforward strategy to introduce the SCF3 moiety into
organic structures in a highly selective manner. However, there
is no report on the transition-metal-catalyzed allylic trifluoro-
methylthiolation reaction to date. Notably, Weng and co-
workers have reported nucleophilic trifluoromethylthiolation of
Special Issue: Mechanisms in Metal-Based Organic Chemistry
Received: August 21, 2014
© XXXX American Chemical Society
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dx.doi.org/10.1021/jo5019393 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
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a
Table 1. Optimization of the Reaction Conditions
b
entry
1
2
catalyst
solvent
time (h)
yield (%)
1
1a
1a
1a
1a
1a
1a
1b
1a
1a
1a
1a
1a
1a
2a
2a
2b
2c
2c
2c
2c
2c
2c
2c
2c
2d
2d
Pd(PPh3)4 (5 mol %)
[Ru]-1 (1 mol %)
[Ru]-1 (1 mol %)
[Ru]-1 (1 mol %)
[Ru]-2 (1 mol %)
[Ru]-2 (2 mol %)
[Ru]-2 (2 mol %)
[Ru]-2 (2 mol %)
[Ru]-2 (2 mol %)
[Ru]-2 (2 mol %)
[Ru]-2 (2 mol %)
[Ru]-2 (2 mol %)
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
THF
12
12
12
12
12
12
12
12
12
12
12
4
n.d.
2
4a, 17
4a, 14
4a, 68
4a, 65
4a, 80
4a, 31
4a, 8
3
4
5
6
7
8
9
CH2Cl2
c-hexane
toluene
MeCN
MeCN
4a, 44
4a, 26
4a, 20
4a, 89
n.d.
10
11
12
13
24
a
b
Reaction conditions: 1/2 = 2.0/1.0, 0.1 M of 2, 50 °C. Yield determined by 19F NMR of the crude reaction mixture with PhCF3 as an internal
standard.
1). No detrimental effect on the yield was observed with [Ru]-
216 as the catalyst (entry 5, Table 1). We chose [Ru]-2 as the
catalyst for further reaction condition optimization for its
bench-stable and easy-to-handle characteristics. Increasing the
catalyst loading to 2 mol % dramatically accelerated the
reaction rate, thus affording a much higher yield (entry 6, Table
1). Me4NSCF3 (1b) was also tested and turned out to be a less
efficient nucleophilic reagent in this Ru-catalyzed allylic
trifluoromethylthiolation reaction (31% yield, entry 7, Table
1). Various solvents (MeCN, THF, CH2Cl2, c-hexane, and
toluene) were examined, and MeCN was found to be the best
one (entries 6, 8−11, Table 1). The reaction proceeded much
faster when the branched allylic carbonate 2d was used,
providing the trifluoromethylthiolation product 4a up to 89%
yield (entry 12, Table 1). The control experiment in the
absence of Ru catalyst could not afford any of the trifluoro-
methylthiolation product (entry 13, Table 1).
Under the optimal conditions (entry 12, Table 1), the
substrate scope of the Ru-catalyzed regioselective allylic
trifluoromethylthiolation reaction was explored, as summarized
in Table 2. The reaction conditions tolerated a wide range of
allylic substrates, affording the (E)-allylic trifluoromethyl
thioethers exclusively in good to excellent yields. Aryl allylic
carbonates with either electron-donating (4-Me, 4-tBu, 3-Me, 2-
MeO) or electron-withdrawing (4-Br, 4-F, 4-CF3, 3-Br, 3-Cl, 2-
Cl, 2-F, 2,4-Cl2) substituents at the para, meta, or ortho
positions of the aryl ring all afforded their corresponding allylic
trifluoromethyl thioethers in 75−91% yields (4b−4m, entries
2−13, Table 2). 1-Naphthyl substituted allylic trifluoromethyl
thioether 4n could be obtained in 79% yield (entry 14, Table
2). Alkyl substituted allylic carbonates also worked well (entry
15, Table 2). However, the reactions with alkyl substituted
allylic carbonates were much slower. Only 52% yield of 4p and
Table 2. Substrate Scope of Ru-Catalyzed Regioselective
Allylic Trifluoromethylthiolation Reaction
a
entry
product (4)
time (h)
yield (%)
1
2
4a, R = C6H5
4
4
89
91
80
80
82
88
81
79
81
84
75
75
83
79
87
52
55
4b, R = 4-MeC6H4
4c, R = 4-tBuC6H4
4d, R = 4-BrC6H4
4e, R = 4-FC6H4
4f, R = 4-CF3C6H4
4g, R = 3-MeC6H4
4h, R = 3-BrC6H4
4i, R = 3-ClC6H4
4j, R = 2-MeOC6H4
4k, R = 2-ClC6H4
4l, R = 2-FC6H4
4m, R = 2,4-Cl2C6H3
4n, R = 1-naphthyl
4o, R = CH2OBn
4p, R = Bn
3
4
4
4
5
4
6
4
7
4
8
4
9
4
10
11
12
13
14
15
4
4
4
4
4
4
b
16
b
24
24
17
4q, R = BnCH2
a
b
Reaction conditions: 1a/2/[Ru]-2 = 2.0/1.0/0.02, 0.5 mmol scale. 5
mol % of [Ru]-2 was used.
55% yield of 4q could be obtained, even by increasing the
catalyst loading to 5 mol % (entries 16 and 17, Table 2).
Mechanistic Study. The Ru-catalyzed allylic substitution
reactions generally afford branched products with high
regioselectivity13 with few exceptions.17 Therefore, the
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complete formation of the linear (E)-allylic trifluoromethyl
thioethers suggests a second allylic trifluoromethylthiolation
might occur, after the initial substitution step.18 The branched
allylic trifluoromethyl thioether 3 would act as a potential
electrophile, leading to the thermodynamically more stable
linear allylic counterpart 4 (Scheme 1).
Scheme 1. Proposed Mechanism of the Ru-Catalyzed Allylic
Trifluoromethylthiolation Reaction
In order to test this hypothesis, we employed the allylic
trifluoromethyl thioether 4a as the electrophile in the Ru-
catalyzed allylic substitution reaction. The linear allylic
trifluoromethyl thioether 4a turned out to be a suitable
electrophile as the reaction proceeded with benzyl amine or
NaCH(CO2Me)2 as the nucleophile, though only in moderate
conversions (eq 1). It is well-known that the branched allylic
Figure 2. Plot of product distribution vs reaction conversion.
EXPERIMENTAL SECTION
■
General Methods. Unless stated otherwise, all reactions were
carried out in flame-dried glassware under an argon atmosphere. All
solvents were purified and dried according to standard methods prior
to use.
1H NMR spectra were obtained at 300 or 400 MHz and recorded
relative to the tetramethylsilane signal (0 ppm) or residual protio-
solvent. 13C NMR spectra were obtained at 75 or 100 MHz, and
chemical shifts were recorded relative to the solvent resonance
(CDCl3, 77.0 ppm). 19F NMR spectra were obtained at 282 or 376
precursors with a terminal double bond are more reactive in the
transition-metal-catalyzed allylic substitution reaction than
linear ones. Therefore, it is reasonable that the initial formed
branched allylic trifluoromethyl thioether 3 would further react
with 1a in the presence of the Ru-catalyst, giving the
thermodynamically more stable linear allylic trifluoromethyl
thioether 4 (Scheme 1).
1
MHz and recorded relative to CFCl3 (0 ppm). Data for H NMR are
recorded as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d
= doublet, t = triplet, m = multiplet or unresolved, br = broad singlet,
coupling constant(s) in Hz, integration). Data for 13C NMR are
reported in terms of chemical shift (δ, ppm). The ruthenium complex
[Ru]-2,16 trifluoromethylthiolation reagents (CsSCF3, Me4NSCF3),12
and substituted allylic carbonates19 were prepared according to the
known procedures.
General Procedure for Ru-Catalyzed Allylic Trifluorome-
thylthiolation. CsSCF3 (234 mg, 1.0 mmol), [Ru]-2 (5.95 mg, 0.01
mmol), allylic carbonate 2 (0.50 mmol), and CH3CN (5.0 mL) were
added to a reaction tube equipped with a magnetic stir bar under
argon. The tube was then placed into a preheated 50 °C oil bath. After
the reaction was complete (monitored by TLC), the crude reaction
mixture was filtrated through Celite and washed with n-pentane. The
solvents were removed under reduced pressure (>200 Pa). Then, the
residue was purified by silica gel column chromatography to afford
product 4 with n-pentane.
1
The in situ H NMR monitoring of the reaction process
(molar ratio of 1a:2d = 1:1) at room temperature provided
further evidence supporting the mechanistic hypothesis. The
plots of product distribution during the conversion of 2d to 4a
at room temperature are depicted in Figure 2. This process
follows the proposed reaction pathway that the initially formed
branched allylic trifluoromethyl thioether 3a would further
react with CsSCF3, leading to the linear product 4a. The plot
(blue one) clearly shows that the relative concentration of B/L
goes down along with reaction time. From these results, we
anticipate that a proper transition metal that could catalyze the
first allylic trifluoromethylthiolation while not the second
substitution reaction might provide the allylic trifluoromethyl
thioether with highly branched regioselectivity.
4a.9 Colorless oil, 110.3 mg, 89% yield. 1H NMR (400 MHz,
CDCl3) δ 3.68 (d, J = 7.6 Hz, 2H), 6.20 (dt, J = 15.6, 7.2 Hz, 1H),
6.57 (d, J = 16.0 Hz, 1H), 7.21−7.27 (m, 1H), 7.28−7.33 (m, 2H),
7.33−7.38 (m, 2H); 19F NMR (376 MHz, CDCl3) δ −40.8 (s).
4b.9 Colorless oil, 129.0 mg, 91% yield. 1H NMR (400 MHz,
CDCl3) δ 2.33 (s, 3H), 3.70 (d, J = 7.2 Hz, 2H), 6.16 (dt, J = 15.6, 7.6
Hz, 1H), 6.55 (d, J = 15.6 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H), 7.26 (d, J
= 8.0 Hz, 2H); 19F NMR (376 MHz, CDCl3) δ −38.4 (s).
4c.9 Colorless oil, 116.3 mg, 80% yield. 1H NMR (300 MHz,
CDCl3) δ 1.31 (s, 9H), 3.70 (d, J = 7.2 Hz, 2H), 6.17 (dt, J = 15.3, 7.5
Hz, 1H), 6.57 (d, J = 15.6 Hz, 1H), 7.26−7.41 (m, 4H); 19F NMR
(282 MHz, CDCl3) δ −39.6 (s).
CONCLUSION
■
In summary, we have developed a highly efficient Ru-catalyzed
regioselective allylic trifluoromethylthiolation reaction. This
reaction merits a broad substrate scope and good to excellent
yields, providing linear (E)-allylic trifluoromethyl thioethers
exclusively. Mechanistic investigation revealed that this reaction
proceeds via a double allylic trifluoromethylthiolation sequence.
Further expanding the substrate scope and tuning the reaction
into a branch selective manner are in progress in our lab.
C
dx.doi.org/10.1021/jo5019393 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
4d.9 Colorless oil, 116.3 mg, 80% yield. 1H NMR (400 MHz,
CDCl3) δ 3.68 (d, J = 7.2 Hz, 2H), 6.20 (dt, J = 15.6, 8.4 Hz, 1H),
6.51 (d, J = 15.6 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 7.43 (d, J = 8.0 Hz,
1H); 19F NMR (376 MHz, CDCl3) δ −40.8 (s).
1471, 1258, 1097, 1048, 1013, 868, 803, 756; MS (EI, m/z): 286 (M+);
HRMS (EI-TOF) calcd for C10H7F3SCl2 (M+): 285.9598. Found:
285.9600.
4n. Colorless oil, 105.1 mg, 79% yield. 1H NMR (400 MHz,
CDCl3) δ 3.74 (d, J = 7.2 Hz, 2H), 6.18 (dt, J = 15.2, 8.0 Hz, 1H),
7.29 (d, J = 15.2 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 7.43−7.55 (m, 3H),
7.75 (d, J = 8.0 Hz, 1H), 7.81 (dd, J = 7.6, 2.4 Hz, 1H), 8.01 (d, J = 8.0
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 32.8 (CH2), 123.5 (CH),
124.2 (CH), 125.6 (CH), 125.9 (CH), 126.2 (CH), 126.4 (CH),
128.4 (CH), 128.5 (CH), 131.0, 131.6 (CH), 131.7 (q, J = 305.2 Hz,
1C), 133.5, 133.8; 19F NMR (376 MHz, CDCl3) δ −40.6 (s); IR (thin
film): νmax (cm−1) = 3047, 2930, 1591, 1509, 1238, 1107, 961, 795,
775, 755; MS (EI, m/z): 268 (M+); HRMS (EI-TOF) calcd for
C14H11F3S (M+): 268.0534. Found: 268.0537.
4e. Colorless oil, 101.3 mg, 82% yield. 1H NMR (400 MHz,
CDCl3) δ 3.68 (d, J = 7.6 Hz, 2H), 6.12 (dt, J = 15.2, 7.6 Hz, 1H),
6.51 (d, J = 15.6 Hz, 1H), 7.00 (t, J = 8.8 Hz, 2H), 7.32 (dd, J = 8.8,
5.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 32.6 (CH2), 115.6 (CH,
d, J = 21.6 Hz, 2C), 122.8 (CH, d, J = 1.9 Hz, 1C), 128.1 (CH, d, J =
8.2 Hz, 2C), 130.8 (q, J = 304.9 Hz, 1C), 132.2 (CH, d, J = 3.4 Hz,
1C), 133.1, 162.6 (d, J = 246.1 Hz, 1C); 19F NMR (376 MHz, CDCl3)
δ −40.9 (s), −113.5 (m); IR (thin film): νmax (cm−1) = 3042, 1602,
1508, 1231, 1147, 1100, 963, 768, 679; MS (EI, m/z): 236 (M+);
HRMS (EI-TOF) calcd for C10H8F4S (M+): 236.0283. Found:
236.0282.
4o. Colorless oil, 102.2 mg, 87% yield. 1H NMR (300 MHz,
CDCl3) δ 3.53 (d, J = 5.1 Hz, 2H), 4.00 (d, J = 3.6 Hz, 2H), 4.50 (s,
2H), 5.71−5.92 (m, 2H), 7.23−7.41 (m, 5H); 13C NMR (75 MHz,
CDCl3) δ 31.6 (CH2, d, J = 2.3 Hz, 1C), 69.5 (CH), 72.2 (CH), 126.5
(CH), 127.6 (CH), 127.7 (CH), 128.4 (CH), 130.7 (q, J = 305.1 Hz,
1C), 131.5 (CH), 137.9; 19F NMR (282 MHz, CDCl3) δ −39.7 (s);
IR (thin film): νmax (cm−1) = 3032, 2854, 1496, 1361, 1243, 1102,
1028, 966, 735, 665; MS (ESI): 280 (M + NH4)+; HRMS (ESI-TOF)
calcd for C12H17F3NOS (M + NH4)+: 280.0977. Found: 280.0983.
4p. Colorless oil, 66.9 mg, 52% yield. 1H NMR (400 MHz, CDCl3)
δ 3.38 (d, J = 6.8 Hz, 2H), 3.53 (d, J = 7.6 Hz, 2H), 5.58 (dt, J = 14.4,
6.8 Hz, 1H), 5.86 (dt, J = 14.4, 6.0 Hz, 1H), 7.14−7.19 (d, J = 7.6 Hz,
2H), 7.19−7.24 (m, 1H), 7.24−7.33 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 32.1 (CH2, d, J = 2.3 Hz, 1C), 38.6 (CH), 124.9 (CH),
126.3 (CH), 128.4 (CH), 128.5 (CH), 130.8 (q, J = 308.2 Hz, 1C),
134.4 (CH), 139.4; 19F NMR (376 MHz, CDCl3) δ −40.9 (s); IR
(thin film): νmax (cm−1) = 3064, 1665, 1494, 1241, 1101, 1030, 967,
745, 697; MS (EI, m/z): 232 (M+); HRMS (EI-TOF) calcd for
C11H11F3S (M+): 232.0534. Found: 232.0532.
4f.9 Colorless oil, 127.5 mg, 88% yield. 1H NMR (300 MHz,
CDCl3) δ 3.71 (d, J = 7.5 Hz, 2H), 6.32 (dt, J = 15.3, 7.8 Hz, 1H),
6.61 (d, J = 15.6 Hz, 1H), 7.45 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.4 Hz,
2H); 19F NMR (282 MHz, CDCl3) δ −39.6 (s), −61.4 (s).
4g.9 Colorless oil, 92.1 mg, 81% yield. 1H NMR (400 MHz,
CDCl3) δ 2.33 (s, 3H), 3.67 (d, J = 7.2 Hz, 2H), 6.18 (dt, J = 15.6, 8.0
Hz, 1H), 6.53 (d, J = 16.0 Hz, 1H), 7.06 (d, J = 7.2 Hz, 1H), 7.12−
7.25 (m, 3H); 19F NMR (376 MHz, CDCl3) δ −40.9 (s).
4h. Colorless oil, 117.4 mg, 79% yield. 1H NMR (400 MHz,
CDCl3) δ 3.68 (d, J = 7.6 Hz, 2H), 6.21 (dt, J = 15.2, 7.6 Hz, 1H),
6.50 (d, J = 15.6 Hz, 1H), 7.17 (t, J = 8.0 Hz, 1H), 7.25 (t, J = 6.4 Hz,
1H), 7.38 (d, J = 8.0 Hz, 1H), 7.50 (s, 1H); 13C NMR (100 MHz,
CDCl3) δ 32.4 (CH2), 122.8, 124.8 (CH), 125.1 (CH), 129.3 (CH),
130.1 (CH), 130.7 (q, J = 305.3 Hz, 1C), 130.9 (CH), 132.7 (CH),
138.1; 19F NMR (376 MHz, CDCl3) δ −40.8 (s); IR (thin film): νmax
(cm−1) = 3063, 1591, 1560, 1473, 1207, 1146, 1099, 960, 853, 774,
677; MS (EI, m/z): 296 (M+); HRMS (EI-TOF) calcd for
C10H8F3SBr (M+): 295.9482. Found: 295.9481.
4q. Colorless oil, 69.7 mg, 55% yield. 1H NMR (400 MHz, CDCl3)
δ 2.30−2.45 (m, 2H), 2.69 (t, J = 7.2 Hz, 2H), 3.49 (d, J = 7.2 Hz,
2H), 5.52 (dt, J = 14.4, 7.2 Hz, 1H), 5.74 (dt, J = 14.0, 6.8 Hz, 1H),
7.10−7.23 (m, 3H), 7.23−7.32 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 32.2 (CH2), 34.0 (CH2), 35.3 (CH2), 124.1 (CH), 125.9
(CH), 128.3 (CH), 128.4 (CH), 130.8 (q, J = 304.6 Hz, 1C), 135.1
(CH), 141.4; 19F NMR (376 MHz, CDCl3) δ −41.0 (s); IR (thin
film): νmax (cm−1) = 3029, 2928, 2858, 1605, 1496, 1454, 1242, 1106,
967, 928, 747, 698; MS (EI, m/z): 246 (M+); HRMS (EI-TOF) calcd
for C12H13F3S (M+): 246.0690. Found: 246.0686.
4i.9 Colorless oil, 99.7 mg, 81% yield. 1H NMR (400 MHz, CDCl3)
δ 3.70 (d, J = 7.6 Hz, 2H), 6.24 (dt, J = 15.6, 7.2 Hz, 1H), 6.54 (d, J =
15.6 Hz, 1H), 7.18−7.31 (m, 3H), 7.36 (s, 1H); 19F NMR (376 MHz,
CDCl3) δ −40.9 (s).
4j.9 Colorless oil, 108.1 mg, 84% yield. 1H NMR (400 MHz,
CDCl3) δ 3.73 (d, J = 7.2 Hz, 2H), 3.84 (s, 3H), 6.24 (dt, J = 15.2, 7.6
Hz, 1H), 6.82−6.97 (m, 3H), 7.24 (t, J = 8.4 Hz, 1H), 7.40 (d, J = 7.2
Hz, 1H); 19F NMR (376 MHz, CDCl3) δ −38.4 (s).
4k. Colorless oil, 109.2 mg, 75% yield. 1H NMR (300 MHz,
CDCl3) δ 3.71 (d, J = 7.5 Hz, 2H), 6.18 (dt, J = 15.3, 7.5 Hz, 1H),
6.97 (d, J = 15.6 Hz, 1H), 7.13−7.25 (m, 2H), 7.28−7.37 (m, 1H),
7.43−7.52 (m, 1H); 13C NMR (75 MHz, CDCl3) δ 32.6 (CH2, q, J =
3.8 Hz, 1C), 126.0 (CH), 126.9 (CH), 127.0 (CH), 129.1 (CH),
129.7 (CH), 130.4 (CH), 130.8 (q, J = 305.6 Hz, 1C), 133.1, 134.2;
19F NMR (282 MHz, CDCl3) δ −39.5 (s); IR (thin film): νmax (cm−1)
= 3048, 1592, 1470, 1419, 1239, 1147, 1099, 962, 748, 694; MS (EI,
m/z): 252 (M+); HRMS (EI-TOF) calcd for C10H8F3SCl (M+):
251.9987. Found: 251.9991.
ASSOCIATED CONTENT
* Supporting Information
■
S
NMR spectral data for all the new and known compounds. This
material is available free of charge via the Internet at http://
pubs.acs.org.
4l. Colorless oil, 88.5 mg, 75% yield. 1H NMR (400 MHz, CDCl3)
δ 3.71 (d, J = 7.2 Hz, 2H), 6.31 (dt, J = 15.6, 8.4 Hz, 1H), 6.74 (d, J =
16.0 Hz, 1H), 7.03 (t, J = 8.4 Hz, 1H), 7.09 (t, J = 7.6 Hz, 1H), 7.18−
7.28 (m, 1H), 7.42 (t, J = 7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
δ 32.9 (CH2), 115.8 (d, J = 21.9 Hz, 1C), 123.9 (CH, d, J = 11.9 Hz,
1C), 124.2 (CH, d, J = 3.7 Hz, 1C), 125.7 (CH, d, J = 4.8 Hz, 1C),
126.8 (CH, d, J = 3.0 Hz, 1C), 127.5 (CH, d, J = 3.3 Hz, 1C), 129.4
(CH, d, J = 8.2 Hz, 1C), 130.8 (q, J = 304.9 Hz, 1C), 160.2 (d, J =
248.4 Hz, 1C); 19F NMR (376 MHz, CDCl3) δ −40.9 (s), −117.8
(m); IR (thin film): νmax (cm−1) = 3048, 1612, 1487, 1232, 1147,
1096, 965, 751, 683; MS (EI, m/z): 236 (M+); HRMS (EI-TOF) calcd
for C10H8F4S (M+): 236.0283. Found: 236.0280.
AUTHOR INFORMATION
Corresponding Author
*E-mail: slyou@sioc.ac.cn (S.-L.Y.).
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Basic Research Program of China (973
Program 2015CB856600) and the National Natural Science
Foundation of China (21025209, 21121062, 21332009) for the
generous financial support.
4m. Colorless oil, 134.9 mg, 83% yield. 1H NMR (400 MHz,
CDCl3) δ 3.73 (d, J = 7.2 Hz, 2H), 6.19 (dt, J = 15.2, 7.2 Hz, 1H),
6.91 (d, J = 15.6 Hz, 1H), 7.20 (dd, J = 8.4, 2.4 Hz, 1H), 7.37 (d, J =
2.0 Hz, 1H), 7.43 (d, J = 8.4 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ
32.5 (CH2), 126.6 (CH), 127.3 (CH), 127.7 (CH), 129.3 (CH), 129.4
(CH), 130.7 (q, J = 305.7 Hz, 1C), 132.8, 133.6, 134.1; 19F NMR (376
MHz, CDCl3) δ −40.8 (s); IR (thin film): νmax (cm−1) = 2963, 1587,
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