Stereoselective formation of Z- or E-vinyl thioethers from arylthiols and acetylenes under transition-metal-free conditions

Article abstract of DOI:10.1002/ejoc.201300727

Vinyl sulfide formation with good yield and high regio- and stereoselectivities from thiols and acetylenes under transition-metal-free conditions is described. Potassium phosphate was used as an effective additive to enhance the reaction yield and selecti

Full text of DOI:10.1002/ejoc.201300727

Job/Unit: O30727
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FULL PAPER
DOI: 10.1002/ejoc.201300727
Stereoselective Formation of Z- or E-Vinyl Thioethers from Arylthiols and
Acetylenes under Transition-Metal-Free Conditions
Yunfeng Liao,[a,b] Shanping Chen,[a] Pengcheng Jiang,[a] Hongrui Qi,[a] and
Guo-Jun Deng*[a]
Keywords: Vinylic compounds / Thiols / Alkynes / Regioselectivity / Diastereoselectivity
Vinyl sulfide formation with good yield and high regio- and
stereoselectivities from thiols and acetylenes under transi-
tion-metal-free conditions is described. Potassium phosphate
was used as an effective additive to enhance the reaction
yield and selectivity. Z-Vinyl sulfides were predominately
formed in the presence of potassium phosphate, whereas E-
vinyl sulfides were formed under solvent- and base-free con-
ditions.
Introduction
Vinyl thioethers are very important compounds that have
shown a wide range of biological activities.[1] Vinyl thio-
ethers are also useful synthetic intermediates in organic
transformations.[2] In the light of their importance, the de-
velopment of efficient methods for the synthesis of these
sulfur-containing compounds, with high regio- and stereo-
selectivities, starting from readily available starting materi-
als, has been given considerable attention.[3] The most con-
venient and direct approach to the synthesis of vinyl thio-
ethers is the hydrothiolation of alkynes with thiols
(Scheme 1). Since three possible types of product (i.e., Mar-
kovnikov product A and two anti-Markovnikov products B
and C) could be formed, control of the regio- and stereose-
lectivity of the hydrothiolation reaction is very challenging.
Most of the various hydrothiolation reactions that have
been developed give Markovnikov-type addition. Vinyl sulf-
ides of type A could be selectively obtained in the presence
of transition metal catalysts.
Scheme 1. Hydrothiolation of alkynes with thiols.
Au[11] complexes as catalysts. Zhang,[12] Beletskaya,[13] and
Frech[14] have developed efficient approaches for the selec-
tive preparation of Z-vinyl sulfides (type C) catalyzed by
CuI and [(P{(NC5H10)(C6H11)2})2Pd(Cl)2], respectively.
The selective addition of thiols to alkynes under transition-
metal-free conditions has also been achieved.[15] Dove et al.
reported a solvent-controlled nucleophilic addition reaction
of alkyl thiols to electron-deficient alkynes.[16] Both anti-
Markovnikov thioalkenes and dithianes could be selectively
prepared under organocatalytic conditions. Oshima[17] et al.
synthesized various Z-vinyl sulfides using cesium carbonate
as the only additive and DMSO as the solvent. However,
when thiophenol was used for this reaction, the correspond-
ing product was obtained in only 14% yield and with a
poor E/Z selectivity (12:88). The preparation of vinyl thio-
ethers from arylthiols with high regio- and stereoselectivi-
ties under transition-metal-free conditions is highly desir-
able. Since the combination of the basic additive and the
solvent plays an important role for this kind of reaction, we
envisioned that it might be possible to find a hydrothiol-
ation system for arylthiols by systematic screening of bases
and solvents. In this paper, we report an efficient and highly
selective approach to the preparation of Z-vinyl sulfides
from arylthiols and acetylenes under transition-metal-free
conditions. In addition, E-vinyl sulfides were also synthe-
sized under solvent-free conditions without base.
Palladium,[4] nickel,[5] rhodium,[6] actinides and lantha-
nides,[7] indium,[8] and zirconium[9] complexes have success-
fully been used as catalysts for this reaction. In recent years,
the selective formation of anti-Markovnikov products has
attracted considerable interest. The anti-Markovnikov
products of type B have been obtained using rhodium[10] or
[a] Key Laboratory of Environmentally Friendly Chemistry and
Application of Ministry of Education, College of Chemistry,
Xiangtan University,
Xiangtan 411105, China
E-mail: gjdeng@xtu.edu.cn
http://gjdeng.webs.com
[b] School of Chemistry & Chemical Engineering, Hunan Institute
of Engineering,
Xiangtan 411104, China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300727.
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Y. Liao, S. Chen, P. Jiang, H. Qi, G.-J. Deng
FULL PAPER
replaced with other organic solvents, the reaction yield or
stereoselectivity decreased (Table 1, entries 12–14). A high
yield could be obtained by increasing the reaction tempera-
ture to 100 °C without using an excess of 2a (Table 1, en-
try 15). A moderate yield was observed when the reaction
temperature was decreased to 60 °C (Table 1, entry 16).
Interestingly, the hydrothiolation reaction kept a high
stereoselectivity when the reaction was carried out under an
atmosphere of air (Table 1, entry 17).
After the optimized reaction conditions were established,
we tested a number of substituted benzenethiol derivatives
using ethynylbenzene (2a) as an addition partner (Table 2).
The reactions with benzenethiols bearing electron-donating
groups proceeded smoothly to give the desired (Z)-anti-
Markovnikov products in moderate to high yields and with
excellent regio- and stereoselectivities (Table 2, entries 1–7).
Better yields and higher regio- and stereoselectivities were
Results and Discussion
As shown in Table 1, our investigation began with the
nucleophilic addition of 4-methylbenzenethiol (1a) to eth-
ynylbenzene (2a). When the reaction was carried out in the
absence of any additives at 80 °C under argon, the anti-
Markovnikov vinyl sulfide products were obtained in 90%
yield with a Z/E ratio of 17:83, as determined by GC and
1H NMR methods (Table 1, entry 1). The yield could be
improved to 94% when the reaction temperature was in-
creased to 100 °C (Table 1, entry 2). Various basic potas-
sium salts were investigated using NMP (N-methyl-2-
pyrrolidone) as solvent. The reaction yield did not improve,
but the stereoselectivity improved significantly (Table 1, en-
tries 4–8). Among these salts, anhydrous potassium phos-
phate (K3PO4) showed the best reactivity and stereoselecti-
vity, and the (Z)-anti-Markovnikov product was obtained
in 87% yield with a high Z/E ratio (Ͼ99:1). It is interesting
that decreasing or increasing the amount of potassium
phosphate both resulted in a decrease in the reaction yield
(Table 1, entries 9 and 10). When the ratio of 2a to 1a was
increased to 1.5:1, the reaction yield was further improved
to 95% (Table 1, entry 11). As we previously mentioned, the
solvent plays an important role for the control of stereose-
lectivity in this kind of transformation. When NMP was
Table 2. Reaction of ethynylbenzene (2a) with various thiols.[a]
Table 1. Optimization of the reaction conditions.[a]
[a] Conditions: 1a (0.5 mmol), 2a (0.5 mmol), solvent (2.0 mL),
24 h, under argon, unless otherwise noted. [b] GC yield based on
1a using dodecane as internal standard. [c] The ratio was deter-
mined by 1H NMR spectroscopic analysis. [d] 0.75 mmol 2a was
used. [e] An average result of three runs of the reaction in air.[18]
[a] Conditions: 1 (0.5 mmol), 2a (0.75 mmol), K3PO4 (0.75 mmol),
NMP (2.0 mL), 24 h, 80 °C, under argon. [b] Isolated yield based
on 1. [c] The ratio was determined by 1H NMR spectroscopic
analysis. [d] At 100 °C, 0.5 mmol 2a was used.
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Formation of Z- or E-Vinyl Thioethers
obtained when an amino group was located ortho to the 1a to give 3w in high yield (Table 3, entry 8). Unfortunately,
thiol group (Table 2, entries 6 and 7). In general, the intro- aliphatic alkynes were not suitable for this kind of transfor-
duction of electron-withdrawing substituents on the benz- mation. Only trace amounts of the desired product (i.e., 3x)
enethiols resulted in a decrease in the reaction yields were detected when 1-octyne (2j) was used (Table 3, en-
(Table 2, entries 9–11). However, the reaction of 4-chloro- try 9).
benzenethiol (1l) and 4-bromobenzenethiol (1m) with 2a
Having achieved the selective formation of Z-vinyl sulf-
gave 3l and 3m in 81 and 86% yields, respectively (Table 2, ides using a K3PO4/NMP catalytic system, we focused our
entries 12 and 13). Besides arylthiols, the aliphatic phenyl- efforts on the preparation of E-vinyl thioethers. During the
methanethiol was also reactive, and it gave the correspond- optimization process, we had observed that the hydrothiol-
ing product (i.e., 3o) in 71% yield (Table 2, entry 15).
ation reactions selectively gave E-vinyl thioethers as the
To further examine the scope and the limitations of the major products in the absence of base and solvent (Table 1,
reaction, various aromatic terminal alkynes were treated entry 1). Based on this observation, we investigated the ad-
with 4-methylbenzenethiol (1a) under the optimized condi- dition reaction under solvent-free conditions and in the ab-
tions (Table 3). It was observed that alkynes with alkyl sub- sence of base (Table 4). When 4-methylbenzenethiol (1a) re-
stituents at the para position proceeded smoothly to give acted with ethynylbenzene (2a; 1.0 equiv.) at 100 °C, the de-
the desired products in moderate to good yields (Table 3, sired products (i.e., 4a) were obtained in 88% yield (Table 4,
entries 1–3). However, the stereoselectivity dramatically de- entry 1). Various substituted arylthiols were used under
creased when 1-ethynyl-4-methoxybenzene (2e) was used similar reaction conditions, and the corresponding E-vinyl
(Table 3, entry 4). Halogen-substituted alkynes also could thioethers were obtained in high yields. The position of the
be used for this kind of reaction, and the corresponding subsituents on the thiols slightly affected the stereoselecti-
products were obtained in good yields and with high stereo- vity, and a methyl group at the ortho position gave the prod-
selectivities (Table 3, entries 5–7). To our delight, an in- uct with better selectivity (Table 4, entry 2). Functional
ternal alkyne diphenylacetylene (i.e., 2i) also reacted with groups such as chloro and bromo were well tolerated under
the solvent-free reaction conditions (Table 4, entries 4 and
5). In general, the reaction yields for E-vinyl sulfide forma-
tion were similar to those for Z-vinyl sulfide formation.
However, the stereoselectivity for the E-vinyl sulfide forma-
tion was worse than that for the Z-vinyl sulfide formation.
We found that a radical inhibitor {i.e., TEMPO [(2,2,6,6-
tetramethylpiperidin-1-yl)oxyl]} completely inhibited the
base-free reaction. This indicates that the base-free addition
is a radical reaction.
Table 3. Reaction of 4-methylbenzenethiol (1a) with various acetyl-
enes.[a]
Table 4. (E)-vinyl sulfide formation from acetylenes and thiols.[a]
[a] Conditions: 1a (0.5 mmol), 2 (0.5 mmol), K3PO4 (0.75 mmol),
NMP (2.0 mL), 24 h, 100 °C, under argon. [b] Isolated yield based
on 1a. [c] The ratio was determined by 1H NMR spectroscopic
analysis. [d] At 80 °C, 0.75 mmol 2b was used. [e] At 80 °C,
0.75 mmol 1a was used.
[a] Conditions: 1 (0.5 mmol), 2 (0.5 mmol), 24 h, 100 °C, under ar-
gon. [b] Isolated yield based on 1. [c] The E/Z ratio was determined
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by H NMR spectroscopy.
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Y. Liao, S. Chen, P. Jiang, H. Qi, G.-J. Deng
FULL PAPER
H), 6.46 (d, J = 10.8 Hz, 1 H), 2.35 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 137.4, 136.6, 132.7, 130.5, 129.9, 128.7,
128.3, 127.0, 127.0, 126.5, 21.0 ppm. MS (EI): m/z (%) = 226 (100),
211, 178, 135, 77.
Conclusions
In conclusion, we have reported an efficient anti-Mar-
kovnikov hydrothiolation from acetylenes and arylthiols un-
der transition-metal-free conditions. The choice of base and
solvent significantly affected the selectivity of the reaction.
(Z)-Styryl(m-tolyl)sulfane (3b): The reaction was carried out fol-
lowing method
B with 3-methylbenzenethiol (1b; 58.7 μL,
When potassium phosphate was used as the base in NMP, 0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
the Z-vinyl sulfides were formed in good yields and with
high regio- and stereoselectivities. When the reaction was
carried out under solvent-free conditions and in the basence
of base, E-vinyl sulfides were the major products. Func-
tional groups were well tolerated in both cases. The scope
and synthetic applications of this reaction are under investi-
gation.
oxide (petroleum ether) to give 3b (96.1 mg, 85%, Z/E Ͼ 99:1) as
1
a white oil. H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 7.2 Hz,
2 H), 7.39 (d, J = 7.4 Hz, 2 H), 7.28–7.22 (m, 4 H), 7.09 (d, J =
6.4 Hz, 1 H), 6.59 (d, J = 10.8 Hz, 1 H), 6.51 (d, J = 10.8 Hz, 1
H), 2.36 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 139.0,
136.5, 136.0, 130.7, 129.0, 128.8, 128.3, 128.0, 127.5, 127.1, 127.1,
126.2, 21.3 ppm. HRMS (ESI): calcd. for C15H15OS [M + H]+
227.0888; found 227.0889.
(Z)-Styryl(o-tolyl)sulfane (3c):[14] The reaction was carried out fol-
Experimental Section
lowing method
B with 2-methylbenzenethiol (1c; 58.8 μL,
0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
oxide (petroleum ether) to give 3c (101.7 mg, 90%, Z/E Ͼ 99:1) as
General Information: All reactions were carried out under an
atmosphere of argon unless otherwise noted. Flash chromatog-
raphy was performed on neutral aluminum oxide (100–200 mesh)
or silica gel (200–300 mesh). 1H and 13C NMR spectra (400 and
100 MHz, respectively) were recorded with a Bruker-AV instru-
ment, and were internally referenced to tetramethylsilane or chloro-
form signals. Mass spectra were measured with an Agilent 5975
GC–MS instrument (EI). New compounds were characterized by
1H and 13C NMR spectroscopy, MS, and HRMS. The structures
1
a white oil. H NMR (400 MHz, CDCl3): δ = 7.58 (d, J = 7.2 Hz,
2 H), 7.46–7.38 (m, 3 H), 7.32–7.22 (m, 4 H), 6.59 (d, J = 10.8 Hz,
1 H), 6.38 (d, J = 10.8 Hz, 1 H), 2.45 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 138.8, 136.6, 135.3, 131.1, 130.4, 128.8,
128.3, 127.6, 127.3, 127.0, 126.7, 126.3, 20.7 ppm. MS (EI): m/z
(%) = 226 (100), 211, 178, 135, 77.
1
of known compounds were confirmed by comparing their H and
(Z)-(2,6-Dimethylphenyl)(styryl)sulfane (3d): The reaction was car-
ried out following method B with 2,6-dimethylbenzenethiol (1d;
66.5 μL, 0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol).
The residue was purified by column chromatography on neutral
aluminum oxide (petroleum ether) to give 3d (96.0 mg, 80%, Z/E
13C NMR spectroscopic data and MS data with those reported in
the literature. All reagents were obtained from commercial suppli-
ers and were used without further purification.
General Procedure, Method A: 4-Methylbenzenethiol (1a; 62 mg,
0.5 mmol) was added to a 10 mL reaction tube. The sealed tube
was purged with argon three times, and ethynylbenzene (2a, 55 μL,
0.5 mmol) was added by syringe. The reaction vessel was stirred at
100 °C for 24 h. After cooling to room temperature, the volatiles
were removed under reduced pressure. The residue was purified by
column chromatography on silica gel (petroleum ether) to give de-
sired product 4a (99.5 mg, 88% yield, E/Z = 87:13) as a white oil.
1
Ͼ 99:1) as a white oil. H NMR (400 MHz, CDCl3): δ = 7.60 (d,
J = 7.6 Hz, 2 H), 7.41 (t, J = 7.4 Hz, 2 H), 7.24 (m, 1 H), 7.18–
7.15 (m, 3 H), 6.45 (d, J = 10.8 Hz, 1 H), 5.99 (d, J = 10.8 Hz, 1
H), 2.50 (s, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 142.4,
137.0, 133.9, 128.8, 128.7, 128.4, 128.3, 126.7, 126.6, 125.4,
22.1 ppm. HRMS (ESI): calcd. for C16H17OS [M + O + H]+
257.0995; found 257.0991.
(Z)-(4-Methoxyphenyl)(styryl)sulfane (3e):[14] The reaction was car-
ried out following method B with 4-methoxybenzenethiol (1e;
61.5 μL, 0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol).
The residue was purified by column chromatography on neutral
aluminum oxide (petroleum ether/EtOAc = 20:1) to give 3e
(106.5 mg, 88%, Z/E Ͼ 99:1) as a white solid. 1H NMR (400 MHz,
CDCl3): δ = 7.52 (d, J = 7.2 Hz, 2 H), 7.44–7.37 (m, 4 H), 7.26 (m,
1 H), 6.90 (d, J = 8.0 Hz, 2 H), 6.49 (d, J = 10.8 Hz, 1 H), 6.40 (d,
J = 10.8 Hz, 1 H), 3.82 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 159.5, 136.6, 132.9, 128.7, 128.3, 128.3, 126.9, 126.8, 125.8,
114.8, 55.3 ppm. MS (EI): m/z (%) = 242 (100), 227, 197, 121, 77.
4-(Styrylthio)aniline (3f):[19] The reaction was carried out following
method C with 4-aminobenzenethiol (1f; 62.5 mg, 0.5 mmol) and
ethynylbenzene (2a; 55.0 μL, 0.5 mmol). The residue was purified
by column chromatography on neutral aluminum oxide (petroleum
ether/EtOAc = 5:1) to give 3f (80.6 mg, 71%, Z/E = 94:6) as a
yellow solid. 1H NMR (400 MHz, CDCl3): δ = 7.51 (d, J = 7.2 Hz,
2 H), 7.38 (t, J = 7.4 Hz, 2 H), 7.31–7.22 (m, 3 H), 6.82 (d, J =
15.2 Hz, 0.06 ϫ 1 H), 6.66 (d, J = 8.4 Hz, 2 H), 6.44 (d, J =
10.4 Hz, 0.94 ϫ 1 H), 6.38 (d, J = 10.8 Hz, 0.94 ϫ 1 H), 3.76 (s, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 146.5, 136.7, 134.0,
133.2, 129.4, 128.6, 128.5, 128.2, 126.7, 125.6, 125.0, 123.6,
General Procedure, Method B: Potassium phosphate (159 mg,
0.75 mmol) and 4-methylbenzenethiol (1a, 62 mg, 0.5 mmol) were
added to a 10 mL reaction tube. The sealed tube was purged with
argon three times, and ethynylbenzene (2a, 82.5 μL, 0.75 mmol)
and NMP (2.0 mL) were added by syringe. The reaction vessel was
stirred at 80 °C for 24 h. After cooling to room temperature, the
volatiles were removed under reduced pressure. The residue was
purified by column chromatography on neutral aluminum oxide
(petroleum ether) to give desired product 3a (98.3 mg, 87% yield,
Z/E Ͼ 99:1) as a white solid.
General Procedure, Method C: Potassium phosphate (159 mg,
0.75 mmol) and 4-methylbenzenethiol (1a, 62 mg, 0.5 mmol) were
added to a 10 mL reaction tube. The sealed tube was purged with
argon three times and ethynylbenzene (2a, 55 μL, 0.5 mmol) and
NMP (2.0 mL) were added by syringe. The reaction vessel was
stirred at 100 °C for 24 h. After cooling to room temperature, the
volatiles were removed under reduced pressure. The residue was
purified by column chromatography on neutral aluminum oxide
(petroleum ether) to give desired product 3a (97.1 mg, 86% yield,
Z/E Ͼ 99:1) as a white solid.
(Z)-Styryl(p-tolyl)sulfane (3a):[19] 1H NMR (400 MHz, CDCl3): δ =
7.53 (d, J = 7.2 Hz, 2 H), 7.39–7.16 (m, 7 H), 6.55 (d, J = 10.4 Hz, 1 115.6 ppm. MS (EI): m/z (%) = 227 (100), 193, 182, 106, 77.
4
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Formation of Z- or E-Vinyl Thioethers
(Z)-2-(Styrylthio)aniline (3g):[19] The reaction was carried out fol-
lowing method with 2-aminobenzenethiol (1g; 62.5 mg,
121.6, 115.9 (d, J = 22.0 Hz) ppm. HRMS (ESI): calcd. for
B
C14H12FOS [M + O + H]+ 247.0587; found 247.0586.
0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
oxide (petroleum ether/EtOAc = 10:1) to give 3g (87.4 mg, 77%,
(Z)-(4-Chlorophenyl)(styryl)sulfane (3l):[19] The reaction was carried
out following method B with 4-chlorobenzenethiol (1l; 71.8 mg,
0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
oxide (petroleum ether/EtOAc = 200:1) to give 3l (100.0 mg, 81%,
Z/E Ͼ 99:1) as a white solid. 1H NMR (400 MHz, CDCl3): δ =
7.51 (d, J = 7.2 Hz, 2 H), 7.41–7.27 (m, 7 H), 6.63 (d, J = 10.8 Hz,
1 H), 6.42 (d, J = 10.4 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 136.2, 134.8, 133.3, 131.2, 129.3, 128.8, 128.3, 128.1,
127.3, 125.1 ppm. MS (EI): m/z (%) = 246 (100), 211, 178, 155, 77.
1
Z/E Ͼ 99:1) as a yellow solid. H NMR (400 MHz, CDCl3): δ =
7.55 (d, J = 7.6 Hz, 2 H), 7.41 (m, 3 H), 7.28 (m, 1 H), 7.18 (t, J
= 7.2 Hz, 1 H), 6.77–6.72 (m, 2 H), 6.52 (d, J = 10.8 Hz, 1 H), 6.19
(d, J = 10.8 Hz, 1 H), 4.25 (s, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 147.7, 136.6, 135.2, 130.4, 128.8, 128.3, 127.7, 127.0,
126.7, 118.7, 117.8, 115.3 ppm. MS (EI): m/z (%) = 227, 194, 136
(100), 125, 77.
(4-Bromophenyl)(styryl)sulfane (3m):[19] The reaction was carried
out following method C with 4-bromobenzenethiol (1m; 94.5 mg,
0.5 mmol) and ethynylbenzene (2a; 55.0 μL, 0.5 mmol). The residue
was purified by column chromatography on neutral aluminum ox-
ide (petroleum ether/EtOAc = 20:1) to give 3m (125.1 mg, 86%,
Z/E = 96:4) as a yellow solid. 1H NMR (400 MHz, CDCl3): δ =
7.52–7.31 (m, 9 H), 6.79 (d, J = 8.8 Hz, 0.04 ϫ 1 H), 6.64 (d, J =
10.8 Hz, 0.96 ϫ 1 H), 6.42 (d, J = 10.4 Hz, 0.96 ϫ 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 136.2, 135.4, 132.5, 132.4, 132.2,
131.7, 131.4, 131.1, 130.5, 128.8, 128.7, 128.3, 128.3, 127.4, 127.3,
126.1, 124.9, 124.8, 121.2 ppm. MS (EI): m/z (%) = 292 (100), 247,
211, 178, 77.
(Z)-N-[4-(Styrylthio)phenyl]acetamide (3h): The reaction was car-
ried out following method B with N-(4-mercaptophenyl)acetamide
(1h; 83.5 mg, 0.5 mmol) and ethynylbenzene (2a; 82.5 μL,
0.75 mmol). The residue was purified by column chromatography
on neutral aluminum oxide (petroleum ether/EtOAc = 5:1) to give
3h (99.5 mg, 74%, Z/E Ͼ 99:1) as a white solid. 1H NMR
(400 MHz, CDCl3): δ = 7.51–6.49 (m, 4 H), 7.43–7.26 (m, 5 H),
6.56 (d, J = 10.8 Hz, 1 H), 6.43 (d, J = 10.8 Hz, 1 H), 2.19 (s, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 168.4, 137.4, 136.5, 131.2,
128.7, 128.3, 127.1, 126.9, 126.6, 125.9, 120.6, 24.5 ppm. HRMS
(ESI): calcd. for C16H16NOS [M + H]+ 270.0947; found 270.0943.
(4-Nitrophenyl)(styryl)sulfane (3i):[8] The reaction was carried out
(Z)-Naphthalen-2-yl(styryl)sulfane (3n):[19] The reaction was carried
out following method B with naphthalene-2-thiol (1n; 80 mg,
0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
oxide (petroleum ether/EtOAc = 50:1) to give 3n (96.0 mg, 73%,
Z/E Ͼ 99:1) as a white solid. 1H NMR (400 MHz, CDCl3): δ =
7.93 (s, 1 H), 7.81 (t, J = 9.2 Hz, 3 H), 7.59–7.40 (m, 7 H), 7.29 (d,
J = 7.6 Hz, 1 H), 6.67 (d, J = 10.4 Hz, 1 H), 6.61 (d, J = 10.8 Hz,
1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 136.5, 133.7, 133.5,
132.3, 128.8, 128.7, 128.5, 128.3, 127.7, 127.6, 127.4, 127.2, 126.7,
126.7, 126.2, 126.1, 126.1, 125.7 ppm. MS (EI): m/z (%) = 262
(100), 228, 185, 115, 77.
Benzyl(styryl)sulfane (3o):[19] The reaction was carried out follow-
ing method B with phenylmethanethiol (1o; 58.8 μL, 0.5 mmol) and
ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The residue was purified
by column chromatography on silica gel (petroleum ether) to give
3o (97.0 mg, 86%, Z/E = 77:23) as a white oil. 1H NMR (400 MHz,
CDCl3): δ = 7.46–7.18 (m, 10 H), 6.72 (d, J = 15.6 Hz, 0.23 ϫ 1
H), 6.53 (d, J = 15.6 Hz, 0.23 ϫ 1 H), 6.43 (d, J = 10.8 Hz, 0.77
ϫ 1 H), 6.24 (d, J = 10.8 Hz, 0.77 ϫ 1 H), 4.01–4.00 (d, 0.23 ϫ 2
H, 0.77 ϫ 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.4,
136.9, 129.0, 128.8, 128.7, 128.6, 128.6, 128.2, 128.1, 127.4, 127.3,
127.0, 126.7, 126.0, 125.9, 125.6, 124.4, 39.5 ppm. MS (EI): m/z
(%) = 226 (100), 135, 91, 77, 65.
following method
B with 4-nitrobenzenethiol (1i; 77.5 mg,
0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
oxide (petroleum ether/EtOAc = 200:1) to give 3i (64.3 mg, 50%,
1
Z/E = 90:10) as a yellow solid. H NMR (400 MHz, CDCl3): δ =
8.19 (d, J = 8.4 Hz, 2 H), 7.54–7.30 (m, 7 H), 7.03 (d, J = 15.6 Hz,
0.10 ϫ 1 H), 6.87 (d, J = 10.4 Hz, 0.90 ϫ 1 H), 6.52 (d, J = 10.4 Hz,
0.90 ϫ 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 145.7, 137.9,
135.6, 132.1, 129.0, 128.9, 128.7, 128.4, 128.0, 127.9, 127.1, 126.5,
124.1, 120.6, 118.2 ppm. MS (EI): m/z (%) = 257 (100), 210, 178,
91, 77.
(4-Fluorophenyl)(styryl)sulfane (3j):[20] The reaction was carried out
following method
B with 4-fluorobenzenethiol (1j; 53.3 μL,
0.5 mmol) and ethynylbenzene (2a; 82.5 μL, 0.75 mmol). The resi-
due was purified by column chromatography on neutral aluminum
oxide (petroleum ether/EtOAc = 200:1) to give 3j (70.1 mg, 61%,
Z/E = 95:5) as a white solid. 1H NMR (400 MHz, CDCl3): δ =
7.52–7.38 (m, 6 H), 7.32–7.29 (m, 1 H), 7.06 (t, J = 8.4 Hz, 2 H),
6.82 (d, J = 15.6 Hz, 0.05 ϫ 1 H), 6.57 (d, J = 10.4 Hz, 0.95 ϫ 1
H), 6.40 (d, J = 10.8 Hz, 0.95 ϫ 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 162.4 (d, J = 246.3 Hz), 136.4, 132.6 (d, J = 8.1 Hz),
131.4 (d, J = 3.3 Hz), 128.7, 128.7, 128.3, 127.6, 127.2, 127.2, 126.5,
126.0, 123.9, 116.3 (d, J = 21.3 Hz) ppm. MS (EI): m/z (%) = 230
(100), 196, 185, 139, 77. HRMS (ESI): calcd. for C14H12FOS [M
+ O + H]+ 247.0587; found 247.0585.
(4-Methylstyryl)(p-tolyl)sulfane (3p):[21] The reaction was carried
out following method B with 4-methylbenzenethiol (1a; 62.0 mg,
(2-Fluorophenyl)(styryl)sulfane (3k): The reaction was carried out
0.5 mmol) and
1-ethynyl-4-methylbenzene
(2b;
87.0 mg,
following method
C
with 2-fluorobenzenethiol (1k; 53.3 mg,
0.75 mmol). The residue was purified by column chromatography
on neutral aluminum oxide (petroleum ether/EtOAc = 20:1) to give
3p (72.0 mg, 60%, Z/E = 96:4) as a white solid. 1H NMR
(400 MHz, CDCl3): δ = 7.42 (d, J = 7.6 Hz, 2 H), 7.36 (d, J =
7.6 Hz, 2 H), 7.21–7.14 (m, 4 H), 6.79 (d, J = 15.2 Hz, 0.04 ϫ 1
H), 6.65 (d, J = 15.6 Hz, 0.04 ϫ 1 H), 6.52 (d, J = 10.8 Hz, 0.96
0.5 mmol) and ethynylbenzene (2a; 55.0 μL, 0.5 mmol). The residue
was purified by column chromatography on neutral aluminum ox-
ide (petroleum ether/EtOAc = 200:1) to give 3k (82.8 mg, 72%,
Z/E = 95:5) as a yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.55
(d, J = 7.2 Hz, 2 H), 7.47 (t, J = 7.4 Hz, 1 H), 7.40 (t, J = 7.4 Hz,
2 H), 7.34–7.28 (m, 2 H), 7.17–7.09 (m, 2 H), 6.77 (d, J = 11.2 Hz, ϫ 1 H), 6.40 (d, J = 10.8 Hz, 0.96 ϫ 1 H), 2.36–2.35 (d, 0.96 ϫ 3
0.05 ϫ 1 H), 6.64 (d, J = 10.8 Hz, 0.95 ϫ 1 H), 6.39 (d, J = 10.4 Hz, H, 0.04 ϫ 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.2,
0.95 ϫ 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 160.9 (d, J =
245.9 Hz), 136.2, 132.6, 132.4, 129.3 (d, J = 3.7 Hz), 128.8, 128.7,
128.3, 128.2, 127.7, 127.3, 126.1, 124.7 (d, J = 3.8 Hz), 124.5, 123.2,
136.8, 133.8, 132.9, 131.1, 130.4, 129.9, 129.3, 129.0, 128.7, 126.7,
125.8, 123.0, 21.2, 21.0 ppm. MS (EI): m/z (%) = 240 (100), 225,
192, 135, 91.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O30727
/KAP1
Date: 09-09-13 10:30:40
Pages: 9
Y. Liao, S. Chen, P. Jiang, H. Qi, G.-J. Deng
FULL PAPER
(Z)-(4-Ethylstyryl)(p-tolyl)sulfane (3q): The reaction was carried
out following method C with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-ethyl-4-ethynylbenzene (2c; 70.7 μL, 0.5 mmol).
The residue was purified by column chromatography on neutral
aluminum oxide (petroleum ether) to give 3q (85.0 mg, 67%, Z/E
ϫ 1 H), 6.48 (s, 2 H), 2.35 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 137.6, 135.1, 132.6, 132.3, 131.0, 130.6, 130.0, 129.9,
128.8, 128.4, 128.0, 127.0, 125.7, 125.2, 21.0 ppm. HRMS (ESI):
calcd. for C15H14ClS [M + H]+ 261.0499; found 261.0496.
(Z)-(4-Bromostyryl)(p-tolyl)sulfane (3v): The reaction was carried
out following method C with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-bromo-4-ethynylbenzene (2h; 90.5 mg, 0.5 mmol).
The residue was purified by column chromatography on silica gel
(petroleum ether) to give 3v (131.0 mg, 86%, Z/E Ͼ 99:1) as a white
1
Ͼ 99:1) as a white oil. H NMR (400 MHz, CDCl3): δ = 7.45 (d,
J = 6.0 Hz, 2 H), 7.36 (d, J = 6.0 Hz, 2 H), 7.23–7.15 (m, 4 H),
6.53 (d, J = 10.0 Hz, 1 H), 6.40 (d, J = 10.0 Hz, 1 H), 2.67–2.65
(m, 2 H), 2.35 (s, 3 H), 1.26–1.25 (m, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 143.2, 137.2, 134.1, 132.9, 130.4, 129.9,
128.7, 127.7, 126.6, 125.8, 28.6, 21.0, 15.4 ppm. HRMS (ESI):
calcd. for C17H19OS [M + O + H]+ 271.1151; found 271.1152.
1
solid. H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 8.0 Hz, 2 H),
7.40–7.35 (m, 4 H), 7.17 (d, J = 7.2 Hz, 2 H), 6.50 (d, J = 10.8 Hz,
1 H), 6.45 (d, J = 10.8 Hz, 1 H), 2.36 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 137.6, 135.5, 132.3, 131.7, 131.4, 131.0,
130.6, 130.2, 130.0, 128.4, 128.2, 127.3, 126.0, 125.2, 120.7,
21.0 ppm. HRMS (ESI): calcd. for C15H14BrS [M + H]+ 304.9994;
found 304.9998.
(4-Pentylstyryl)(p-tolyl)sulfane (3r): The reaction was carried out
following method C with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-ethynyl-4-pentylbenzene (2d; 96.0 μL, 0.5 mmol).
The residue was purified by column chromatography on silica gel
(petroleum ether) to give 3r (126.0 mg, 85% Z/E = 93:7) as a white
oil. 1H NMR (400 MHz, CDCl3): δ = 7.44 (d, J = 7.6 Hz, 2 H),
7.36 (d, J = 7.6 Hz, 2 H), 7.21–7.15 (m, 4 H), 6.79 (d, J = 15.2 Hz,
0.07 ϫ 1 H), 6.66 (d, J = 15.2 Hz, 0.07 ϫ 1 H), 6.53 (d, J = 10.4 Hz,
0.93 ϫ 1 H), 6.40 (d, J = 10.4 Hz, 0.93 ϫ 1 H), 2.61 (t, J = 7.6 Hz,
2 H), 2.35 (s, 3 H), 1.62 (m, 2 H), 1.33 (m, 4 H), 0.89 (m, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 142.0, 137.2, 134.0, 132.9,
131.2, 130.4, 130.3, 129.9, 128.7, 128.3, 126.7, 125.9, 125.8, 122.9,
35.7, 31.5, 31.0, 22.5, 21.0, 14.0 ppm. HRMS (ESI): calcd. for
C20H25OS [M + O + H]+ 313.1621; found 313.1624.
(1,2-Diphenylvinyl)(p-tolyl)sulfane (3w): The reaction was carried
out following method C with 4-methylbenzenethiol (1a; 93.0 mg,
0.75 mmol) and 1,2-diphenylethyne (2i; 89.0 mg, 0.5 mmol). The
residue was purified by column chromatography on silica gel (pe-
troleum ether) to give 3w (138.9 mg, 92% Z/E = 89:11) as a white
oil. 1H NMR (400 MHz, CDCl3): δ = 7.74 (d, J = 7.2 Hz, 2 H),
7.62 (d, J = 7.2 Hz, 2 H), 7.38–7.19 (m, 7 H), 7.15 (s, 1 H), 7.08
(d, J = 7.6 Hz, 2 H), 6.91 (d, J = 7.6 Hz, 2 H), 6.64 (s, 0.11 ϫ 1
H), 2.29 (s, 0.11 ϫ 3 H), 2.19 (s, 0.89 ϫ 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 141.1, 136.9, 135.8, 135.4 135.0, 133.1,
131.5, 129.8, 129.5, 129.4, 128.9, 128.4, 128.1, 128.1, 128.0, 127.8,
127.7, 126.7, 20.9 ppm. HRMS (ESI): calcd. for C21H19S
[M + H]+ 303.1202; found 303.1198.
Styryl(p-tolyl)sulfane (4a):[10c] 1H NMR (400 MHz, CDCl3): δ =
7.53 (d, J = 7.2 Hz, 0.13 ϫ 2 H), 7.38–7.15 (m, 9 H), 6.86 (d, J =
15.6 Hz, 0.87 ϫ 1 H), 6.65 (d, J = 15.6 Hz, 0.87 ϫ 1 H), 6.55 (d,
J = 10.4 Hz, 0.13 ϫ 1 H), 6.46 (d, J = 10.4 Hz, 0.13 ϫ 1 H), 2.36
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.3, 136.7,
131.2, 130.6, 130.5, 129.9, 128.7, 128.7, 128.6, 128.3, 128.3, 127.3,
127.0, 126.5, 125.9, 124.5, 21.0 ppm. MS (EI): m/z (%) = 226 (100),
211, 178, 135, 77.
Styryl(o-tolyl)sulfane (4b):[22] The reaction was carried out follow-
ing method A with 2-methylbenzenethiol (1c; 58.8 μL, 0.5 mmol)
and ethynylbenzene (2a; 55 μL, 0.5 mmol). The residue was puri-
fied by column chromatography on silica gel (petroleum ether) to
give 4b (96.0 mg, 85% E/Z = 91:9) as a white oil. 1H NMR
(400 MHz, CDCl3): δ = 7.58 (d, J = 7.2 Hz, 0.09 ϫ 2 H), 7.40–
7.21 (m, 9 H), 6.83 (d, J = 15.2 Hz, 0.91 ϫ 1 H), 6.60 (d, J =
15.2 Hz, 0.91 ϫ 1 H), 6.38 (d, J = 10.8 Hz, 0.09 ϫ 1 H), 2.45–2.42
(d, 0.91 ϫ 3 H, 0.09 ϫ 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 138.8, 136.7, 133.7, 131.2, 131.0, 130.9, 130.4, 128.8, 128.6,
128.3, 127.6, 127.4, 127.4, 127.3, 127.1, 126.7, 126.3, 125.9, 123.4,
20.4 ppm. MS (EI): m/z (%) = 226 (100), 211, 178, 135, 77.
(4-Methoxyphenyl)(styryl)sulfane (4c):[10c] The reaction was carried
out following method A with 4-methoxybenzenethiol (1e; 61.5 μL,
0.5 mmol) and ethynylbenzene (2a; 55 μL, 0.5 mmol). The residue
was purified by column chromatography on silica gel (petroleum
ether/EtOAc = 20:1) to give 4c (104.0 mg, 86% E/Z = 60:40) as a
white oil. 1H NMR (400 MHz, CDCl3): δ = 7.52 (d, J = 7.2 Hz,
0.40 ϫ 2 H), 7.44–7.20 (m, 0.60 ϫ 7 H, 0.40 ϫ 5 H), 6.92–6.88 (m,
0.60 ϫ 2 H, 0.40 ϫ 2 H), 6.82 (d, J = 15.6 Hz, 0.60 ϫ 1 H), 6.53–
6.48 (m, 0.60 ϫ 1 H, 0.40 ϫ 1 H), 6.40 (d, J = 10.8 Hz, 0.4 ϫ 1
H), 3.83–3.82 (d, 0.60 ϫ 3 H, 0.40 ϫ 3 H) ppm. 13C NMR
(4-Methoxystyryl)(p-tolyl)sulfane (3s): The reaction was carried out
following method C with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-ethynyl-4-methoxybenzene (2e; 66.0 mg,
0.5 mmol). The residue was purified by column chromatography on
silica gel (petroleum ether/EtOAc = 200:1) to give 3s (96.2 mg,
1
75%, Z/E = 77:23) as a white solid. H NMR (400 MHz, CDCl3):
δ = 7.48 (d, J = 8.4 Hz, 2 H), 7.36 (d, J = 7.6 Hz, 2 H), 7.15 (d, J
= 7.2 Hz, 2 H), 6.93 (d, J = 8.4 Hz, 2 H), 6.85 (d, J = 8.4 Hz, 0.23
ϫ 1 H), 6.68 (m, 0.23 ϫ 1 H), 6.51 (d, J = 10.4 Hz, 1 H), 6.33 (d,
J = 10.4 Hz, 1 H), 3.83–3.81 (d, 0.77 ϫ 3 H, 0.23 ϫ 3 H), 2.35 (s,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.6, 137.2, 132.9,
131.4 130.3, 130.1, 130.1, 129.9, 129.5, 127.2, 126.4, 124.3, 121.2,
113.7, 55.3, 21.0 ppm. HRMS (ESI): calcd. for C16H17OS
[M + H]+ 257.0995; found 257.0990.
(4-Fluorostyryl)(p-tolyl)sulfane (3t): The reaction was carried out
following method C with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-ethynyl-4-fluorobenzene (2f; 60.0 mg, 0.5 mmol).
The residue was purified by column chromatography on silica gel
(petroleum ether) to give 3t (80.5 mg, 66% Z/E = 97:3) as a white
1
solid. H NMR (400 MHz, CDCl3): δ = 7.50 (t, J = 6.4 Hz, 2 H),
7.36 (d, J = 8.0 Hz, 2 H), 7.17 (d, J = 7.2 Hz, 2 H), 7.07 (t, J =
8.4 Hz, 2 H), 6.77 (d, J = 15.6 Hz, 0.03 ϫ 1 H), 6.60 (d, J =
15.6 Hz, 0.03 ϫ 1 H), 6.50 (d, J = 10.8 Hz, 0.97 ϫ 1 H), 6.43 (d,
J = 10.8 Hz, 0.97 ϫ 1 H), 2.35 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 161.6 (d, J = 245.9 Hz), 137.5, 132.8 (d, J = 3.3 Hz),
132.4 130.7, 130.5, 130.4 (d, J = 7.9 Hz), 130.0, 129.3, 127.4 (d, J
= 7.8 Hz), 126.6 (d, J = 1.9 Hz), 125.5, 124.3 (d, J = 2.2 Hz), 115.6
(d, J = 21.6 Hz), 115.2 (d, J = 21.4 Hz), 21.0 ppm. HRMS (ESI):
calcd. for C15H14FOS [M + O + H]+ 261.0744; found 261.0745.
(4-Chlorostyryl)(p-tolyl)sulfane (3u): The reaction was carried out
following method C with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-chloro-4-ethynylbenzene (2g; 68.3 mg, 0.5 mmol).
The residue was purified by column chromatography on silica gel
(petroleum ether) to give 3u (111.0 mg, 85% Z/E = 98:2) as a white (100 MHz, CDCl3): δ = 159.6, 136.8, 133.4, 132.9, 129.0, 128.7,
1
solid. H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.4 Hz, 2 H), 128.6, 128.3, 128.3, 127.2, 126.9, 125.8, 125.7, 124.6, 114.9,
7.36 (m, 4 H), 7.17 (d, J = 7.6 Hz, 2 H), 6.84 (d, J = 15.2 Hz, 0.02 55.4 ppm. MS (EI): m/z (%) = 242 (100), 227, 197, 121, 77.
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O30727
/KAP1
Date: 09-09-13 10:30:40
Pages: 9
Formation of Z- or E-Vinyl Thioethers
(4-Chlorophenyl)(styryl)sulfane (4d):[10c] The reaction was carried
out following method A with 4-chlorobenzenethiol (1l; 71.8 mg,
0.5 mmol) and ethynylbenzene (2a; 55 μL, 0.5 mmol). The residue
was purified by column chromatography on silica gel (petroleum
ether/EtOAc = 200:1) to give 4d (98.5 mg, 80% E/Z = 66:34) as a
[1]
[2]
a) P. Johannesson, G. Lindeberg, A. Johansson, G. V. Nikiforo-
vich, A. Gogoll, B. Synnergren, M. LeGrèves, F. Nyberg, A.
Karlén, A. Hallberg, J. Med. Chem. 2002, 45, 1767–1777; b)
C. A. Dvorak, W. D. Schmitz, D. J. Poon, D. C. Pryde, J. P.
Lawson, R. A. Amos, A. I. Meyers, Angew. Chem. 2000, 112,
1730–1732; Angew. Chem. Int. Ed. 2000, 39, 1664–1666.
a) R. J. Cremlyn, An Introduction to Organosulfur Chemistry,
John Wiley & Sons, Chichester, UK, 1996; b) B. M. Trost,
A. C. Lavoie, J. Am. Chem. Soc. 1983, 105, 5075–5090; c) D. A.
Singleton, K. M. Church, J. Org. Chem. 1990, 55, 4780–4782;
d) H. Mizuno, K. Domon, K. Masuya, K. Tanino, I. Kuwa-
jima, J. Org. Chem. 1999, 64, 2648–2656; e) N. Muraoka, M.
Mineno, K. Itami, J. Yoshida, J. Org. Chem. 2005, 70, 6933–
6936; f) R. L. A. David, J. A. Kornfield, Macromolecules 2008,
41, 1151–1161; g) M. J. Stanford, A. P. Dove, Macromolecules
2009, 42, 141–147; h) R. J. Pounder, M. J. Stanford, P. Brooks,
S. P. Richards, A. P. Dove, Chem. Commun. 2008, 5158–5160.
a) R. Castarlenas, A. D. Giuseppe, J. J. Perez-Torrente, L. A.
Oro, Angew. Chem. Int. Ed. 2013, 52, 211–222; b) J. Drabowicz,
P. Kielbasinski, M. Mikolajczyk, Science of Synthesis Houben–
Weyl, Methods of Molecular Transformations, Thieme, Stutt-
gart, Germany, 2007, vol. 33, p. 113–169.
1
white solid. H NMR (400 MHz, CDCl3): δ = 7.51 (d, J = 7.2 Hz,
0.34 ϫ 2 H), 7.41–7.31 (m, 9 H), 6.82 (d, J = 15.2 Hz, 0.66 ϫ 1
H), 6.74 (d, J = 15.6 Hz, 0.66 ϫ 1 H), 6.63 (d, J = 10.8 Hz, 0.34
ϫ 1 H), 6.42 (d, J = 10.8 Hz, 0.34 ϫ 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 136.3, 134.8, 133.9, 133.3, 133.1, 132.8,
131.3, 131.0, 129.3, 128.8, 128.7, 128.3, 128.1, 127.8, 127.3, 126.1,
126.1, 125.1, 122.6 ppm. MS (EI): m/z (%) = 246 (100), 211, 178,
121, 77.
(4-Bromophenyl)(styryl)sulfane (4e):[10c] The reaction was carried
out following method A with 4-bromobenzenethiol (1m; 94.5 mg,
0.5 mmol) and ethynylbenzene (2a; 55 μL, 0.5 mmol). The residue
was purified by column chromatography on silica gel (petroleum
ether/EtOAc = 20:1) to give 4e (117.8 mg, 81% E/Z = 72:28) as a
[3]
[4]
1
white solid. H NMR (400 MHz, CDCl3): δ = 7.52–7.28 (m, 9 H),
6.82 (d, J = 15.6 Hz, 0.72 ϫ 1 H), 6.76 (d, J = 15.6 Hz, 0.72 ϫ 1
H), 6.64 (d, J = 10.8 Hz, 0.28 ϫ 1 H), 6.42 (d, J = 10.4 Hz, 0.28
ϫ 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 136.3, 135.5, 134.6,
133.0, 132.2, 132.2, 131.4, 131.2, 128.8, 128.7, 128.3, 127.9, 127.4,
126.1, 124.9, 122.3, 121.2, 120.9 ppm. MS (EI): m/z (%) = 292
(100), 245, 211, 134, 77.
a) H. Kuniyasu, A. Ogawa, K. Sato, I. Ryu, N. Kambe, N.
Sonoda, J. Am. Chem. Soc. 1992, 114, 5902–5903; b) A. Ogawa,
T. Ikeda, K. Kimura, T. Hirao, J. Am. Chem. Soc. 1999, 121,
5108–5114; c) M. Takenori, D. Masayuki, N. Akihiro, O.
Akiya, Bull. Chem. Soc. Jpn. 2011, 84, 413–415.
[5]
[6]
D. A. Malyshev, N. M. Scott, N. Marion, E. D. Stevens, V. P.
Ananikov, I. P. Beletskaya, S. P. Nolan, Organometallics 2006,
25, 4462–4470.
(4-Chlorostyryl)(p-tolyl)sulfane (4f):[22] The reaction was carried out
following method A with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-chloro-4-ethynylbenzene (2g; 68.3 mg, 0.5 mmol).
The residue was purified by column chromatography on silica gel
(petroleum ether) to give 4f (109.0 mg, 84% E/Z = 83:17) as a white
a) C. Cao, L. R. Fraser, J. A. Love, J. Am. Chem. Soc. 2005,
127, 17614–17615; b) L. R. Fraser, J. Bird, Q. Wu, C. Cao,
B. O. Patrick, J. A. Love, Organometallics 2007, 26, 5602–5611;
c) J. Yang, A. Sabarre, L. R. Fraser, B. O. Patrick, J. A. Love,
J. Org. Chem. 2009, 74, 182–187; d) A. D. Giuseppe, R. Cas-
tarlenas, J. J. Pérez-Torrente, M. Crucianelli, V. Polo, R. San-
cho, F. J. Lahoz, L. A. Oro, J. Am. Chem. Soc. 2012, 134, 8171–
8183; e) H. Zhao, J. Peng, M. Z. Cai, Catal. Lett. 2012, 142,
138–142.
a) C. J. Weiss, S. D. Wobser, T. J. Marks, J. Am. Chem. Soc.
2009, 131, 2062–2063; b) C. J. Weiss, S. D. Wobser, T. J. Marks,
Organometallics 2010, 29, 6308–6320.
R. Sarma, N. Rajesh, D. Prajapat, Chem. Commun. 2012, 48,
4014–4106.
1
solid. H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.0 Hz, 0.17
ϫ 2 H), 7.34–7.16 (m, 8 H), 6.84 (d, J = 15.6 Hz, 0.83 ϫ 1 H), 6.54
(d, J = 15.2 Hz, 0.83 ϫ 1 H), 6.48 (s, 0.17 ϫ 2 H), 2.36 (s, 0.83 ϫ
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.6, 135.3, 132.9,
131.0, 130.6, 130.0, 129.9, 128.8, 128.5, 128.5, 128.0, 127.0, 125.8,
125.2, 21.1 ppm. MS (EI): m/z (%) = 260 (100), 245, 215, 135, 91.
[7]
(4-Bromostyryl)(p-tolyl)sulfane (4g): The reaction was carried out
following method A with 4-methylbenzenethiol (1a; 62.0 mg,
0.5 mmol) and 1-bromo-4-ethynylbenzene (2h; 90.5 mg, 0.5 mmol).
The residue was purified by column chromatography on silica gel
(petroleum ether) to give 4g (126.5 mg, 83%, E/Z = 93:7) as a white
[8]
[9]
C. J. Weiss, T. J. Marks, J. Am. Chem. Soc. 2010, 132, 10533–
10546.
1
solid. H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 8.4 Hz, 0.07
[10]
a) A. Ogawa, T. Ikeda, K. Kimura, T. Hirao, J. Am. Chem.
Soc. 1999, 121, 5108–5114; b) S. Shoai, P. Bichler, B. Kang, H.
Buckley, J. A. Love, Organometallics 2007, 26, 5778–5781; c) Y.
Yang, R. M. Rioux, Chem. Commun. 2011, 47, 6557–6559.
A. Corma, C. González-Arellano, M. Iglesias, F. Sánchez,
Appl. Catal. A 2010, 375, 49–54.
ϫ 2 H), 7.42–7.16 (m, 8 H), 6.86 (d, J = 15.2 Hz, 0.93 ϫ 1 H), 6.42
(d, J = 15.6 Hz, 0.93 ϫ 1 H), 2.36 (s, 0.93 ϫ 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 137.6, 135.7, 131.7, 131.4, 131.1, 130.6,
130.6, 130.2, 130.0, 130.0, 128.4, 127.3, 126.0, 121.0, 21.1 ppm. MS
(EI): m/z (%) = 306 (100), 291, 192, 134, 91.
[11]
[12]
S. N. Riduan, J. Y. Ying, Y. Zhang, Org. Lett. 2012, 14, 1780–
1783.
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the 1H and 13C NMR spectra of the compounds
described. HRMS spectra for new compounds.
[13]
[14]
[15]
I. G. Trostyanskaya, I. P. Beletskaya, Synlett 2012, 23, 535–540.
R. Gerber, C. M. Frech, Chem. Eur. J. 2012, 18, 8901–8905.
For early examples using base as catalyst, see: a) W. E. Truce,
J. A. Simms, M. M. Boudakian, J. Am. Chem. Soc. 1956, 78,
695–696; b) W. E. Truce, J. A. Simms, J. Am. Chem. Soc. 1956,
78, 2756–2759; c) W. E. Truce, G. J. W. Tichenor, J. Org. Chem.
1972, 37, 2391–2396; d) Y. Takikawa, K. Shimada, H. Matsum-
oto, Chem. Lett. 1983, 1351–1354; e) M. S. Silva, R. G. Lara,
J. M. Marczewski, R. G. Jacob, E. J. Lenardão, G. Perin, Tetra-
hedron Lett. 2008, 49, 1927–1930.
V. X. Truong, A. P. Dove, Angew. Chem. Int. Ed. 2013, 52,
4132–4136.
A. Kondoh, K. Takami, H. Yorimitsu, K. Oshima, J. Org.
Chem. 2005, 70, 6468–6473.
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (NSFC) (21172185), the Hunan Provincial Natural
Science Foundation of China (11JJ1003, 12JJ7002), the New Cen-
tury Excellent Talents in University from the Ministry of Education
of China (NCET-11-0974), and the Research Fund for the Doc-
toral Program of Higher Education of China, Ministry of Educa-
tion of China (20124301110005).
[16]
[17]
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Date: 09-09-13 10:30:40
Pages: 9
Y. Liao, S. Chen, P. Jiang, H. Qi, G.-J. Deng
FULL PAPER
[18] When the reaction was set up under an air atmosphere, the
reproducibility was not very good. Sometimes the reaction gave
the product with Z/E Ͼ 99:1, and sometimes the reaction gave
the product with only Z/E = 96:1. 97:1 is an average of three
runs of the reaction.
[20] Y. F. Zheng, X. F. Du, W. L. Bao, Tetrahedron Lett. 2006, 47,
1217–1220.
[21] S. Bhadra, B. C. Ranu, Can. J. Chem. 2009, 87, 1605–1609.
[22] V. Baliah, T. K. Rathinasamy, Indian J. Chem. 1971, 9, 220–
225.
[19] S. Ranjit, X. G. Liu, Z. Y. Duan, P. F. Zhang, Org. Lett. 2010,
Received: May 17, 2013
Published Online: ᭿
12, 4134–4136.
8
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O30727
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Date: 09-09-13 10:30:40
Pages: 9
Formation of Z- or E-Vinyl Thioethers
Vinyl Sulfides
Y. Liao, S. Chen, P. Jiang, H. Qi,
G.-J. Deng* ....................................... 1–9
Stereoselective Formation of Z- or E-Vinyl
Thioethers from Arylthiols and Acetylenes
under Transition-Metal-Free Conditions
Z-Vinyl sulfides were formed in good yields
and with high regio- and stereoselectivities
when potassium phosphate was used as
base in N-methyl-2-pyrrolidone. E-Vinyl
sulfides were the major products when the
reaction was carried out under solvent-free
conditions without any base.
Keywords: Vinylic compounds / Thiols /
Alkynes / Regioselectivity / Diastereoselec-
tivity
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