Stereoselective synthesis of (Z)-1,2-diarylthio-1-alkene via the reaction of diaryl disulfides with terminal alkynes catalyzed by cesium hydroxide

Article abstract of DOI:10.1080/00397910802654831

In the presence of a catalytic amount of cesium hydroxide under a nitrogen atmosphere, terminal alkynes reacted with diaryl disulfides at room temperature in dimethylformamide to give almost exclusively (Z)-1,2-diarylthio-1-alkene in good yields, but unde

Full text of DOI:10.1080/00397910802654831

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Stereoselective Synthesis of
(Z)-1,2-Diarylthio-1-alkene
via the Reaction of Diaryl
Disulfides with Terminal
Alkynes Catalyzed by Cesium
Hydroxide
Kang Bing Zou a , Xian Hong Yin b , Wen Qi Liu b ,
Ren Hua Qiu a , Ruo Xin Li a , Ling Ling Shao a , Yin
Hui Li a , Xin Hua Xu a & Rong Hua Yang a
a College of Chemistry and Chemical Engineering ,
Hunan University , Changsha, China
b Department of Chemistry , Xiangnan University ,
Chenzhou, China
Published online: 16 Jun 2009.
To cite this article: Kang Bing Zou , Xian Hong Yin , Wen Qi Liu , Ren Hua Qiu ,
Ruo Xin Li , Ling Ling Shao , Yin Hui Li , Xin Hua Xu & Rong Hua Yang (2009)
Stereoselective Synthesis of (Z)-1,2-Diarylthio-1-alkene via the Reaction of Diaryl
Disulfides with Terminal Alkynes Catalyzed by Cesium Hydroxide, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 39:14, 2464-2471, DOI: 10.1080/00397910802654831
To link to this article: http://dx.doi.org/10.1080/00397910802654831

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Synthetic Communications1, 39: 2464–2471, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802654831
Stereoselective Synthesis of (Z)-1,2-Diarylthio-
1-alkene via the Reaction of Diaryl
Disulfides with Terminal Alkynes Catalyzed
by Cesium Hydroxide
Kang Bing Zou,1 Xian Hong Yin,2 Wen Qi Liu,2
Ren Hua Qiu,1 Ruo Xin Li,1 Ling Ling Shao,1 Yin Hui Li,1
Xin Hua Xu,1 and Rong Hua Yang1
1College of Chemistry and Chemical Engineering, Hunan University,
Changsha, China
2Department of Chemistry, Xiangnan University, Chenzhou, China
Abstract: In the presence of a catalytic amount of cesium hydroxide under a
nitrogen atmosphere, terminal alkynes reacted with diaryl disulfides at room tem-
perature in dimethylformamide to give almost exclusively (Z)-1,2-diarylthio-1-
alkene in good yields, but under an air atmosphere, the reaction gave a mixture
of alkynyl sulfide and (Z)-1,2-diarylthio-1-alkene.
Keywords: Cesium hydroxide, diaryl disulfide, (Z)-1,2-diarylthio-1-alkene,
terminal alkyne
Many different classes of organochalcogen compounds have been
prepared and studied to date. For their syntheses, vinyl sufides have been
used extensively because vinyl sulfides can be conveniently converted to
functional alkenes[1,2] stereoselectively. Among the common vinyl
sulfides, 1,2-dithio-1-alkenes are of much importance because of their
use as bidentante ligands in coordination chemistry, precursors of new
optical materials for microelectronics,[1] and important intermediates for
Received September 15, 2008.
Address correspondence to Xin Hua Xu and Rong Hua Yang, College of
Chemistry and Chemical Engineering, Hunan University, Changsha 410082,
China. E-mail: xhx1581@yahoo.com.cn; yangrh@pku.edu.cn
2464

Cesium Hydroxide Catalysis
2465
organic synthesis. Traditionally there are two kinds of paths for the
preparation of 1,2-dithio-1-alkenes: one involves the addition of
disulfides to terminal alkynes[3–11] and the other is the addition of thiol
to alkynyl sulfides.[12–17] In most cases, both methods need
transition-metal catalysis. In this article, we report a stereoselective synth-
esis of (Z)-1,2-diarylthio-1-alkenes via cesium hydroxide–catalyzed reac-
tion of disulfides with terminal alkynes.
Cesium base has received increasing interest in the past few years. It
has been shown recently that cesium hydroxide could catalyze the
reaction of terminal alkynes with aldehydes and ketones to give pro-
pargyl alcohols, with nitriles to give unsaturated adduct,[18] and with
phenylselenyl bromide to give alkynyl selenides.[19] Our group also
reported that cesium hydroxide–catalyzed addition of diaryldiselenides
to terminal alkynes under N2 gave (Z)-1,2-bis(arylseleno)-1-alkenes[20]
selectively and the reaction of diarylditelluride with terminal alkynes
under an air atmosphere gave alkynyl tellurides.[21] Lothar et al. have also
reported that in the presence of K2CO3 and a catalytic amount of
copper(I), diphenyl disulfide and ditelluride reacted with terminal alkynes
to give alkynyl sulfides and tellurides.[22] These results prompted us to
investigate the reaction of diaryl disulfides with terminal alkynes in the
presence of a catalytic amount of cesium hydroxide.
We first tested the reactions of 3-methyoxy propyne with diphenyl
disulfide. The experiment showed that under an air atmosphere,
3-methyoxy propyne (2.2 mmol) reacted with diphenyl disulfide
(1.0 mmol) in the presence of cesium hydroxide (0.2 mmol) at room
temperature in dimethylformamide (DMF) to give a 6:4 mixture of
3-methyoxy propynyl phenylsulfide and Z-1,2-diphenylthio-3-methyoxy
propene in 81% yield. Though the yield is satisfactory, the selectivity is
not. However, much to our delight, it gave almost exclusively (Z)-
1,2-diphenylthio-3-methyoxy propene in 80% yield when the reaction
Table 1. Reaction of terminal alkynes with diaryl
disulfides to synthesize (Z)-1,2-diarylthio-1-alkenes
Entry
R
Ar
Yields (%)
3a
3b
3c
3d
3e
3f
HO(CH3)2C
HOCH2
CH3OCH2
CH3OCH2
PhOCH2
PhOCH2
Ph
Ph
p-CH3C6H4
Ph
p-CH3C6H4
Ph
61
69
82
77
75
73
71
p-CH3C6H4
Ph
3g

2466
K. B. Zou et al.
Scheme 1. The synthesis of (Z)-1,2-diarylthio-1-alkenes.
was run under N2. We reasoned that if the reaction was performed under
an air atmosphere, some sulfide ions would be transformed into the start-
ing disulfides because of air oxidation, and the reaction would give a
mixture of alkynyl sulfide and (Z)-1,2-diarylthio-1-alkene. Therefore it
is important to run the reaction in the absence of air. With the fine-tuned
method in hand, we set out to investigate the scope of the reaction. A
variety of (Z)-1,2-diarylthio-1-alkenes were synthesized by reacting
different alkynes with diphenyldisulfide or di(p-methylphenyl)disulfide
(Scheme 1), and the results are summarized in Table 1.
A possible reaction mechanism for the reaction of terminal alkynes
with diaryl disulfides is depicted in Scheme 2. First, terminal alkynes
reacted with cesium hydroxide to give cesium alkynides and H2O.
Second, the alkynides reacted with diaryl disulfides to form alkynyl sul-
fides and cesium arylsulfides. Finally, the cesium arylsulfides underwent
nucleophilic addition to the alkynyl sulfides to give the desired
(Z)-1,2-diarylthio-1-alkenes.
To shed some light on the reaction mechanism, the reaction of
p-CH3C6H4SCs with 3-methoxy propanyl phenylsulfide in DMF at room
Scheme 2. The mechanism for the reaction of terminal alkynes with diaryl disulfides.

Cesium Hydroxide Catalysis
2467
Scheme 3. The addition of p-CH3C6H4SCs to 3-methoxy propynyl phenylsulfide.
temperature was performed. The fact that 1-phenylthio-2-
(p-methylphenyl)thio-3-methoxy propene was isolated in almost 100%
yield proved that (Z)-1,2-diarylthio-1-alkene was indeed produced
through the alkynylsulfide intermediate (Scheme 3).
The analysis of 1H NMR and 13C NMR spectra showed that all vinyl
sulfides prepared presented data in full agreement with their assigned
structures. The stereochemistry of trisubstituted alkenes were determined
by nuclear Overhauser effect (NOE) experiments. For example, when
compound 3c was irradiated at the peak of vinylic proton (6.99 ppm),
6% enhancement of CH2 (3.94 ppm) was observed, showing a cis relation
between them.
In conclusion, a mild, efficient, and selective method for the stereo-
selective synthesis of (Z)-1,2-diarylthio-1-akenes was developed. Compared
with the known methods, our methods use only a catalytic amount of
cesium hydroxide and require neither the preparation of alkynyl sulfides
nor the use of expensive transition metals. It could provide a new and
expedient way for the preparation of (Z)-1,2-diarylthio1-1-alkenes.
EXPERIMENTAL
1H NMR and 13C NMR spectra were recorded on a Bruker Advance 400
spectrometer in CDCl3 with tetramethylsilane (TMS) as the internal stan-
dard, chemical shifts are quoted and J values are given in hertz, and ele-
mental analyses were performed on a Yanaco MT-3CHN elemental
analyser. Mass spectra were determined on an HP5989A spectrometer.
Reactions were monitored by thin-layer chromatography (TLC) using
silica-gel F254 aluminum sheets.
General Procedure for the Reaction of Terminal Alkyne with
Diaryl Disulfide to Synthesize (Z)-1,2-Diarylthio-1-alkene
Diaryl disulfides (1.0 mmol) and cesium hydroxide (0.2 mmol) were
added to a solution of alkyne (2.2 mmol) in DMF (5.0 mL). The reaction
mixture was stirred at room temperature under a nitrogen atmosphere for

2468
K. B. Zou et al.
30 h. Then 20 mL of water was added to the residue and extracted with
petroleum ether (3 ꢀ 10 ml). The combined organic phase was dried over
anhydrous Na2SO4 and concentrated under vacuum. The residue was
purified by flash chromatography on silica gel, giving 3a–3g.
Data
Compound 3a
1
(Z)-1,2-Bis(phenylthio)-3-hydroxy-3-methyl-1-butene: H NMR 1.46 (s,
6H), 2.28 (s, 1H), 7.12–7.42 (m, 11H); 13C NMR 29.3, 75.1, 125.4,
127.0, 127.5, 128.8, 129.0, 130.2, 134.8, 134.9, 135.1, 137.7; Ms (m=z):
302 (Mþ). Anal. calcd. for C17H18OS2: C, 67.5; H, 6.00; found: C, 67.3;
H, 6.01.
Compound 3b
1
(Z)-1,2-Bis(p-methylphenylthio)-3-hydroxy-1-propene: H NMR 2.18 (s,
1H), 2.33 (s, 3H), 2.34 (s, 3H), 4.10 (s, 2H), 6.98 (t, J ¼ 1.02 Hz, 1H),
7.10 (d, J ¼ 8.0 Hz, 2H), 7.12 (d, J ¼ 8.0 Hz, 2H), 7.45 (d, J ¼ 8.0 Hz,
2H), 7.47 (d, J ¼ 8.0 Hz, 2H);13C NMR 21.1, 67.4, 124.6, 126.5, 130.1,
130.2, 132.2, 132.9, 133.4, 137.7, 137.9; Ms (m=z): 302 (Mþ). Anal. calcd.
for C17H18OS2: C, 67.5; H, 6.00; found: C, 67.3; H, 6.02.
Compound 3c
(Z)-1,2-Bis(phenylthio)-3-methoxy-1-propene: 1H NMR 3.30 (s, 3H),
3.94 (s, 2H), 6.99 (s, 1H), 7.21–7.36 (m, 6H), 7.40 (d, J ¼ 8.0 Hz, 2H),
7.45 (d, J ¼ 8.0 Hz, 2H); 13C NMR 58.0, 74.4, 126.8, 127.1, 127.3,
129.0, 129.1, 130.0, 130.3, 133.3, 134.6, 134.9; Ms (m=z): 288 (Mþ). Anal.
calcd. for C16H16OS2: C, 66.6; H, 5.59; found: C, 66.7; H, 5.58.
Compound 3d
(Z)-1,2-Bis(p-methylphenylthio)-3-methoxy-1-propene: 1H NMR: 2.33
(s, 3H), 2.35 (s, 3H), 3.26 (s, 3H), 3.91 (s, 2H), 6.95 (t, J ¼ 1.02 Hz,
1H), 7.10 (d, J ¼ 8.0 Hz, 2H), 7.13 (d, J ¼ 8.4 Hz, 2H), 7.45 (d, J ¼ 8.0 Hz,
Hz, 2H), 7.47 (d, J ¼ 8.4 Hz, 2H); 13C NMR 21.1, 57.8, 76.5, 124.9, 126.8,
129.0, 130.0, 130.1, 132.9, 133.1, 133.3, 137.6, 137.8; Ms (m=z): 316 (Mþ).
Anal. calcd. for C18H20OS2: C, 68.3; H, 6.37; found: C, 68.5; H, 6.38.

Cesium Hydroxide Catalysis
2469
Compound 3e
(Z)-1,2-Bis(phenylthio)-3-phenoxy-1-propene: 1H NMR 4.57 (s, 2H),
6.79 (d, J ¼ 8.0 Hz, 2H), 6.93 (t, J ¼ 7.2 Hz, 1H), 7.23 (t, J ¼ 8.0 Hz,
2H), 7.28–7.29 (m, 6H), 7.47 (s, 1H), 7.49–7.51 (m, 2H), 7.57–7.60
(m, 2H); 13C NMR 72.0, 114.8, 121.1, 127.1, 127.5, 128.5, 129.2, 129.3,
129.3, 130.4, 132.6, 132.7, 134.0, 157.9; Ms (m=z): 350 (Mþ). Anal. calcd.
for C21H18OS2: C, 72.0; H, 5.18; found: C, 71.9; H, 5.19.
Compound 3f
1
(Z)-1,2-Bis(p-methylphenylthio)-3-phenoxy-1-propene: H NMR 2.33 (s,
6H), 4.53 (s, 2H), 6.78 (d, J ¼ 8.0 Hz, 2H), 6.92 (t, J ¼ 6.8 Hz, 1H), 7.09
(d, J ¼ 8.0 Hz, 4H), 7.20–7.25 (m, 2H), 7.38 (m, 3H), 7.48 (d, J ¼ 6.8 Hz,
2H); 13C NMR 21.4, 72.3, 115.2, 121.3, 124.9, 127.1, 127.4, 129.6, 130.4,
130.4, 133.3, 133.5, 133.8, 138.0, 138.1, 158.3; Ms (m=z): 378 (Mþ). Anal.
calcd. for C23H22OS2: C, 72.9; H, 5.86; found: C, 72.8; H, 5.87.
Compound 3g
(Z)-1,2-Bis(phenylthio)styrene: 1H NMR 7.07 (s, 1H), 7.21–7.34 (m, 9H),
7.42–7.50 (m, 6H); 13C NMR 126.0, 126.5, 127.4, 127.6, 128.2, 128.6,
128.8, 129.2, 129.3, 130.5, 134.5, 135.2, 136.4, 138.7; Ms (m=z): 320
(Mþ). Anal. calcd. for C20H16S2: C, 74.9; H, 5.03; found: C, 75.1; H, 5.27.
ACKNOWLEDGMENTS
Projects 20372020 and 02JJY4053 were supported by the National
Nature Science Foundations of China and Hunan, respectively.
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