CuI/L-proline-catalyzed synthesis of vinyl sulfides in 95% alcohol

Article abstract of DOI:10.1080/00397910802222746

A method for the synthesis of vinyl sulfides using the simple CuI/L-proline as a catalyst system is reported. The best yields were obtained in the 95% ethanol with 10 mol% CuI, 20 mol% L-proline, and 1.2 equiv of K2CO3. The amino acids act as base and excellent promoter for the copper-catalyzed coupling reactions, and this protocol tolerates both aromatic and heterocyclic thiols and avoids using other expensive additives. Copyright ? Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802222746

This article was downloaded by: [Ams/Girona*barri Lib]
On: 08 October 2014, At: 06:37
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
CuI/L-Proline-Catalyzed
Synthesis of Vinyl Sulfides in
95% Alcohol
Sheng-Rong Guo a & Yan-Qin Yuan a
a Department of Chemistry , Lishui University ,
Lishui, China
Published online: 25 Aug 2010.
To cite this article: Sheng-Rong Guo & Yan-Qin Yuan (2008) CuI/L-Proline-Catalyzed
Synthesis of Vinyl Sulfides in 95% Alcohol, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 38:16, 2722-2730,
DOI: 10.1080/00397910802222746
To link to this article: http://dx.doi.org/10.1080/00397910802222746
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,

and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communications1, 38: 2722–2730, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910802222746
CuI/L-Proline-Catalyzed Synthesis of Vinyl
Sulfides in 95% Alcohol
Sheng-Rong Guo and Yan-Qin Yuan
Department of Chemistry, Lishui University, Lishui, China
Abstract: A method for the synthesis of vinyl sulfides using the simple CuI=
L-proline as a catalyst system is reported. The best yields were obtained in the
95% ethanol with 10 mol% CuI, 20 mol% L-proline, and 1.2 equiv of K2CO3.
The amino acids act as base and excellent promoter for the copper-catalyzed
coupling reactions, and this protocol tolerates both aromatic and heterocyclic
thiols and avoids using other expensive additives.
Keywords: Cross-coupling reaction, L-proline, thiols, vinyl sulfide
Vinyl sulfides play an important role as synthetic intermediates in organic
chemistry. They are equivalents of carbonyl compounds and can be
transformed to sulfoxides and sulfones. Methods for the formation of
vinyl–sulfur bonds are indispensable tools in synthetic chemistry. Their
importance stems from the prevalence of vinyl sulfides in many molecules
that are of biological, pharmaceutical, and materials interest.[1–5]
Because of the importance of these compounds, there have been a
number of reported methods for synthesizing vinyl sulfides.[6,7] Among
them, the addition of thiols to alkynes by free radical conditions or by
anionic addition is one of the most straightforward methods of obtaining
vinyl sulfides,[8,9] affording the anti-Markovnikov product, usually as a
stereoisomeric mixture. The Wittig reaction has also been utilized in
the synthesis of vinyl sulfides, but this method requires the use of strong
bases, and the synthesis of the appropriate Wittig reagents can be prob-
lematic.[10,11] The cross-coupling reaction of vinyl halides with metal
thioalkoxides in the presence of a transition-metal catalyst,[12–14] as well
Received in the U.K. September 10, 2007
Address correspondence to Guo Sheng-rong, Department of Chemistry, Lishui
University, Lishui, China. E-mail: guosr9608@163.com
2722

Vinyl Sulfide Synthesis
2723
Scheme 1.
as the reaction of vinyl halides with sodium and lithium thiols or their tin
analogs cross-coupling on organic halides in the presence of the catalyst
Cu(phen)(PPh3)2NO3,[15] is also one of the most valuable protocols to
gain the vinyl sulfides. However, the scope and functional group toler-
ance of these cross-coupling reactions have not been fully explored.
Recently there has been a resurgence in interest in developing
L-proline-catalyzed cross-coupling reactions. The amino acid proline is
a remarkable molecule that has become important in cross-coupling reac-
tion catalysis.[16–19] Ma and Cai[17] recently reported that CuI=L-proline
(or N-methylglycine) is an efficient catalytic system to make Ullmann-
type arylamination work at mild conditions, and Zheng et al.[20] reported
that the CuI=L-proline system in ionic liquid can promote the cross-
coupling reaction of vinyl bromides and thiols with K2CO3 as the base
at 110ꢀC, but they used expensive ionic liquids as solvents. These
copper-based methods work extremely well with soft nucleophiles such
as amino, sulfur, selenium, and phosphorus. Because of the importance
of vinyl sulfides and the lack of a general protocol for their synthesis,
we now report a general method for the cross-coupling of vinyl iodides
and thiols, using CuI=L-proline as the catalyst, K2CO3 as the base, and
95% alcohol as solvent to synthesize vinyl sulfides (Scheme 1).
The optimization process was performed using the cross-coupling of
4-fluorothiophenol and 3-iodo-cyclohexenone. We first explored the
coupling reaction catalyzed by 10 mol% CuI and 20 mol% L-proline in
alcohol at reflux in the presence of K2CO3. The reaction proceeded well,
and the vinyl sulfide was obtained in good yield. Then we scanned the
effects of bases, using 10 mol% CuI and 10 mol% L-proline as catalyst.
Bases such as K2CO3, K3PO4, and Cs2CO3 were very effective. Other
bases such as Et3N, pyridine, piperidine, and DBU (1,8-diazabicy-
clo[5.4.0]undec-7-ene) were less effective (Table 1). We also observed
the impact of solvents and found that the DMF, DMSO, glycol, and
ionic liquid [Bmim]BF4 were also good solvents for the coupling reaction,
but the best yield and the simplest method to separate the product used
95% alcohol.
Thus, the optimized reaction conditions utilized 10 mol% CuI,
20 mol% L-proline, and 1.2 equiv of K2CO3 in 10 ml of 95% EtOH at

2724
S.-R. Guo and Y.-Q. Yuan
Table 1. Effects of bases and solvents on the coupling of 4-flurothiophenol and
3-iodo-cyclohexenone catalyzed by 10 mol% CuI and 20 mol% L-prolinea
Entry
Base
Solvent
Yieldb (%)
1
2
3
4
5
6
7
8
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
K3PO4
Et3N
95% EtOH
DMF
DMSO
92
86
83
84
85
93
86
54
28
35
42
glycol
[Bmim]BF4
95% EtOH
95% EtOH
95% EtOH
95% EtOH
95% EtOH
95% EtOH
9
10
11
DBU
Pyridine
Piperidine
aReaction conditions: 10 mol% CuI, 20 mol% L-proline, and 1.2 equiv of
K2CO3 in 5–10 ml above solvent at 80ꢀC under N2 atmosphere.
bIsolated yields after reaction 8 h.
reflux under an N2 atmosphere. In the first part of this study, these reac-
tion conditions were applied to the coupling of various functionalized
thiophenol and 3-iodo-cyclohexenone (Table 2).
As can be seen, both electron-rich aromatic (or electron-poor) and
heterocyclic thiols can be coupled to 3-iodo-cyclohexenone in good
yields; however, in contrast to the coupling of aryl and alkanethiols,
the coupling reactions were slower. The thiohydroxyl is more active than
the hydroxyl. The structure of product 3f proved to be the sulfide by
1
comparing the H NMR spectra of 3f with the raw material 2-ethyl-4-
mercaptophenol; the aryl thiols containing -OH (compound 3f) were
efficiently converted to the product (Scheme 2), but of the aryl thiols con-
taining –NH2 (compound 3m) only 40% were converted to the product.
A second part of this work involved the application of different
amino acids as the catalyst. Amino acids can act both as acid and base
and can also facilitate chemical transformations in concert, similar to
enzymatic catalysis. Another virtue of amino acids is the excellent ability
to complex to Cu(I) salt. In this reaction, we also used the L-proline as an
additive. Some other amino acids or other additives were also screened
and proven effective, but best yield was obtained when L-proline was
the additive. If no amino acid was added, the reaction time and yield were
not perfect (Table 3).
In conclusion, we have developed a CuI- and L-proline-catalyzed sys-
tem for the synthesis of vinyl sulfides in good yields using a combination
of 10 mol% CuI and 20 mol% L-proline in 95% ethanol. This method

Vinyl Sulfide Synthesis
2725
Table 2. Coupling reaction of 3-iodo-cyclohexenone with various aryl thiols
catalyzed by CuI=L-proline systema
Product
ArSH
Time (h)
Yieldb (%)
3a
3b
3c
3d
3e
3fc
3g
3h
3i
3j
3k
3l
3mc
3n
3o
4-Flurothiophenol
3-Flurothiophenol
2-Flurothiophenol
3,5-Diflurothiophenol
4-Trifluoromethoxythiophenol
2-Ethyl-4-mercapto-phenol
(4-Bromo-phenyl)-methanethiol
2-Isopropylthiophenol
2,6-Dimethylthiophenol
2-Ethoxythiophenol
2,6-Bistrifluoromethylthiophenol
3-Ethylthiophenol
4-Amino-2-fluoro-thiophenol
Thiazole-2-thiol
Pyrimidine-2-thiol
6
6
6
8
8
4
8
4
4
4
9
6
6
12
12
92
90
88
84
80
82
85
91
88
92
78
82
40
85
87
aReaction conditions: 3-iodo-cyclohexenone (2.0 mmol), 4-flurothiophenol
(2.0 mmol), 10 mol% CuI, 20 mol% L-proline, and 1.2 equiv of K2CO3 in 10 ml
of 95% EtOH at reflux under N2 atmosphere.
bIsolated yields.
cFunctional group is –SH.
tolerates a wide range of functional groups and substrates. We have also
demonstrated the ability to couple both arylthiols and heterocyclic thiols
to vinyl iodide and the catalytic efficiency of different amino acids.
Additionally, the reaction avoids the use of high-boiling-point solvents
such as DMF, DMSO, and [Bmim]BF4 and does not require the use of
expensive palladium and=or air-sensitive additives.
EXPERIMENTAL
1H NMR spectra were recorded on Bruker Avance-300 spectrometer with
TMS as internal standard. IR spectra were determined on Vector-55
Scheme 2.

2726
S.-R. Guo and Y.-Q. Yuan
Table 3. Effect of different a-amino acids in the coupling of 3-iodo-cyclohexe-
none with 4-flurothiophenol reflux in 95% ethanol
Entry
Additive
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
L-Proline
L-Glycine
6
8
8
9
8
8
8
16
92
84
85
73
52
75
25
55
N-Methylglycine
l-Lysine
Ethane-1,2-diamine
Triphenyl-phosphane
None
None
instrument. Elemental analyses were conducted using a Yanaco MT-
5CHN elemental analyzer. Silica gel GF254 was used for analytical
and preparative thin-layer chromotography (TLC). All products were
characterized by comparison with authentic samples using IR,
1H NMR, and MS.
General Procedure for the Synthesis of 3a–l
We placed 10 mL of 95% ethanol and 2.4 mmol of K2CO3 in a 25-mL
beaker, refluxing for 30 min under N2 atmosphere and then cooling to
room temperature. Then 2 mmol of 3-iodo-cyclohexenone, 2 mmol of
thiophenol, 10 mol% CuI, and 20 mol% L-proline were added to the mix-
ture. The mixture in beaker was allowed to stir for a few minutes until it
was homogeneous, and then it was refluxed 4–6 h. The cooled mixture
was filtered with suction, the mixture was concentrated under reduced
pressure, and the residue was purified by column chromatography on sil-
ica gel with cyclohexane and ethyl acetate (V:V ¼ 10:1) as eluent.
Data
1
3-(4-Fluoro-phenylsulfanyl)-cyclohex-2-enone (3a): yellow oil. H NMR
(CDC13): d ¼ 7.43–7.49 (m, 2H), 7.09–7.16 (m, 2H), 5.41 (s, 1H), 2.50–
2.54 (t, J ¼ 6.14, 2H), 2.36–2.38 (t, J ¼ 6.91, 2H), 2.01–2.09 (m, 2H);
IR (film): n ¼ 3002, 1650, 1570, 1405, 1285, 978; MS (70 eV) m=z (%):
222 (Mþ , 18), 154 (100), 109 (78), 77 (65), 58 (45), 28 (55). Anal. calcd.
for C12H11FOS: C, 64.84; H, 4.99; found: C, 64.76; H, 4.88.
3-(3-Fluoro-phenylsulfanyl)-cyclohex-2-enone (3b): yellow oil. 1H
NMR (CDC13): d ¼ 7.51–7.59 (m, 3H), 7.19–7.24 (m, 1H), 5.35 (s, 1H),

Vinyl Sulfide Synthesis
2727
2.45–2.50 (t, J ¼ 6.18, 2H), 2.32–2.36 (t, J ¼ 6.85, 2H), 2.03–2.12 (m,
2H); IR (film): n ¼ 2982, 1652, 1571, 1450, 780; MS (70 eV) m=z (%):
222 (Mþ , 36), 153 (100), 108 (58), 76 (75), 58 (42), 28 (85). Anal. calcd.
for C12H11FOS: C, 64.84; H, 4.99; found: C, 64.97; H, 4.90.
3-(2-Fluoro-phenylsulfanyl)-cyclohex-2-enone (3c): yellow oil. 1H
NMR (CDC13): d ¼ 7.53–7.62 (m, 3H), 7.16–7.26 (m, 1H), 5.23 (s,
1H), 2.46–2.52 (t, J ¼ 6.15, 2H), 2.36–2.42 (t, J ¼ 6.81, 2H), 2.13–2.18
(m, 2H); IR (film): n ¼ 3109, 1650, 1500, 1450, 958, 750; MS (70 eV)
m=z (%): 222 (Mþ , 75), 153 (100), 111 (45), 76 (55), 58 (25), 28 (65).
Anal. calcd. for C12H11FOS: C, 64.84; H, 4.99; found: C, 64.77; H, 5.09.
1
3-(3,5-Difluoro-phenylsulfanyl)-cyclohex-2-enone (3d): yellow oil. H
NMR (CDC13): d ¼ 7.03–7.07 (m, 2H), 6.89–6.95 (m, 1H), 5.53 (s,
1H), 2.51–2.55 (m, 2H), 2.38–2.43 (m, 2H), 2.03–2.11 (m, 2H); IR (film):
n ¼ 3082, 2945, 1650, 1574, 1427, 1285, 1119, 983, 671; MS (70 eV) m=z
(%): 241 ([M þ 1]þ , 11), 240 (Mþ , 79), 172 (100), 112 (68), 95 (82), 72
(75), 58 (65), 15 (46). Anal. calcd. for C12H10F2OS: C, 59.99; H, 4.20;
found: C, 60.17; H, 4.19.
3-(4-Trifluoromethoxy-phenylsulfanyl)-cyclohex-2-enone (3e): yellow
1
oil. H NMR (CDC13): d ¼ 7.51–7.54 (q, J ¼ 8.7, 2H), 7.26–7.28 (q,
J ¼ 8.5, 2H), 5.46 (s, 1H), 2.51–2.55 (t, J ¼ 6.14, 2H), 2.36–2.41 (t,
J ¼ 6.81, 2H), 2.04–2.10 (m, 2H); IR (film): n ¼ 3182, 2900, 1580,
1524, 1401, 985; MS (70 eV) m=z (%): 289 ([M þ 1]þ , 13), 288 (Mþ ,
82), 234 (85), 220 (100), 90 (65), 65 (55). Anal. calcd. for C13H11F3O2S:
C, 54.16; H, 3.85; found: C, 54.24; H, 3.91.
3-(3-Ethyl-4-hydroxy-phenylsulfanyl)-cyclohex-2-enone (3f): white
ꢀ
1
solid, mp 67–69 C. H NMR (CDC13): d ¼ 8.24 (s, 1H), 7.18 (s, 1H),
6.93–7.00 (m, 1H), 6.59–6.61 (dd, J ¼ 8.2, 1H), 5.47 (s, 1H), 2.48–2.59
(m, 4H), 2.22–2.29 (m, 2H), 1.94–2.04 (m, 2H), 1.09–1.31 (m, 3H); IR
(KBr): n ¼ 3321, 3107, 2956, 1567, 1485, 1420, 976; MS (70 eV) m=z
(%): 249 ([M þ 1]þ , 8), 248 (Mꢁ, 100), 179 (89), 104 (54), 91 (76), 64
(45), 58 (45), 28 (35). Anal. calcd. for C14H16O2S: C, 67.71; H, 6.49;
found: C, 67.84; H, 6.50.
3-(4-Bromo-benzylsulfanyl)-cyclohex-2-enone (3 g): yellow oil. 1H
NMR (CDC13): d ¼ 7.40–7.48 (dd, J ¼ 8.02, 2H), 7.19–7.29 (dd,
J ¼ 6.85, 2H), 5.90 (s, 1H), 3.98 (s, 2H), 2.36–2.48 (m, 4H), 2.00–2.08
(m, 2H); IR (film): n ¼ 3044, 2934, 2858, 1645, 1565, 1186, 886; MS
(70 eV) m=z (%): 298 (Mþ , 100), 296 (89), 230 (87), 228 (65), 203 (72),
170 (82), 91 (87), 72 (53), 64 (35), 58 (55), 28 (51). Anal. calcd. for
C13H13BrOS: C, 52.53; H, 4.41; found: C, 52.44; H, 4.50.
3-(2-Isopropyl-phenylsulfanyl)-cyclohex-2-enone (3 h): yellow oil. 1H
NMR (CDC13): d ¼ 7.40–7.42 (m, 3H), 7.19–7.21 (m, 1H), 5.34 (s, 1H),
3.45–3.51 (m, 1H), 2.55 (t, J ¼ 6.57, 2H), 2.34–2.36 (m, J ¼ 6.98, 2H), 2.04
(m, 2H), 1.21 (s, 3H), 1.18 (s, 3H); IR (film): n ¼ 2956, 2923, 1655, 1572,

2728
S.-R. Guo and Y.-Q. Yuan
1380, 1000, 880, 749; MS (70 eV) m=z (%): 247 ([M þ 1]þ , 17), 246 (Mþ ,
100), 194 (56), 178 (84), 118 (76), 91 (77), 72 (45), 58 (55), 28 (48), 15 (68).
Anal. calcd. for C15H18OS: C, 73.13; H, 7.36; found: C, 73.03; H, 7.40.
1
3-(2,6-Dimethyl-phenylsulfanyl)-cyclohex-2-enone (3i): yellow oil. H
NMR (CDC13): d ¼ 7.04–7.28 (m, 3H), 5.24 (s, 1H), 2.53–2.62 (t,
J ¼ 6.53, 2H), 2.38 (s, 6H), 2.35–2.37 (t, J ¼ 6.64, 2H), 2.01–2.16 (m,
2H); IR (film): n ¼ 3356, 3092, 2921, 1658, 1523, 1380, 840, 723; MS
(70 eV) m=z (%): 233 ([M þ 1]þ , 8), 232 (Mþ , 62), 179 (51), 164 (100),
105 (74), 104 (71), 92 (73), 58 (42), 15 (61). Anal. calcd. for C14H16OS:
C, 72.37; H, 6.94; found: C, 72.19; H, 6.86.
3-(2-Ethoxy-phenylsulfanyl)-cyclohex-2-enone (3j): yellow oil. 1H
NMR (CDC13): d ¼ 7.37–7.44 (m, 2H), 6.92–6.98 (t, J ¼ 7.80, 2H),
5.46 (s, 1H), 4.03–4.10 (dd, 2H), 2.51–2.53 (t, J ¼ 6.01, 2H), 2.37–2.55
(t, J ¼ 6.27, 2H), 1.99–2.08 (m, 2H), 1.18–1.42 (m, 3H); IR (film):
n ¼ 3247, 3021, 1651, 1571, 1381, 1027, 882; MS (70 eV) m=z (%): 249
([M þ 1]þ , 11), 248 (Mþ , 71), 196 (77), 180 (100), 121 (57), 91 (78), 66
(65), 58 (55), 28 (54). Anal. calcd. for C14H16O2S: C, 67.71; H, 6.49;
found: C, 67.69; H, 6.56.
3-(2,6-Bis-trifluoromethyl-phenylsulfanyl)-cyclohex-2-enone (3k): yel-
1
low oil. H NMR (CDC13): d ¼ 7.96 (s, 1H), 7.40–7.48 (m, 2H), 5.40
(s, 1H), 2.55–2.62 (m, 2H), 2.41–2.43 (m, 2H), 2.06–2.14 (m, 2H); IR
(film): n ¼ 3052, 2942, 1649, 1584, 1434, 1106, 905, 702; MS (70 eV)
m=z (%): 341 ([M þ 1]þ , 6), 340 (Mþ , 54), 287 (65), 272 (100), 212
(52), 196 (77), 121 (57), 94 (78), 66 (65), 58 (55). Anal. calcd. for
C14H10F6OS: C, 49.41; H, 2.96; found: C, 49.29; H, 2.86.
3-(3-Ethyl-phenylsulfanyl)-cyclohex-2-enone (3 l):yellow oil. 1H NMR
(CDC13): d ¼ 7.27–7.29 (m, 1H), 7.21–7.24 (m, 1H), 6.85–6.89 (m, 2H),
5.12 (s, 1H), 2.63–2.65 (m, 2H), 2.31–2.43 (m, 4H), 1.96–2.04 (m, 2H),
1.28–1.30 (m, 3H); IR (film): n ¼ 3258, 3088, 2902, 1608, 1545, 1104,
924, 701; MS (70 eV) m=z (%): 233 ([M þ 1]þ , 14), 232 (Mþ , 34), 179
(67), 164 (100), 106 (54), 91 (68), 58 (51), 28 (65). Anal. calcd. for
C14H16OS: C, 72.37; H, 6.94; found: C, 72.31; H, 6.85.
3-(4-Amino-2-fluoro-phenylsulfanyl)-cyclohex-2-enone
(3 m):
1H
NMR (CDC13): d ¼ 7.07–7.12 (m, 1H), 6.98–7.02 (m, 1H), 6.61–6.67
(m, 1H), 5.42 (s, 1H), 3.72 (b 2H), 2.58–2.61 (m, 2H),2.35–2.38 (m,
2H), 2.02–2.05 (m, 2H); IR (film): n ¼ 3458, 3356, 3012, 2812, 1635,
1505, 924, 771; MS (70 eV) m=z (%): 238 ([M þ 1]þ , 13), 237 (Mþ ,
52), 184 (78), 168 (100), 110 (84), 92 (46), 65 (28), 58 (59). Anal. calcd.
for C12H12FNOS: C, 60.74; H, 5.10; found: C, 61.06; H, 5.05.
3-(Thiazol-2-ylsulfanyl)-cyclohex-2-enone (3n): 1H NMR (CDC13):
d ¼ 7.97–7.98 (d, J ¼ 3.45, 1H), 7.63–7.64 (d, J ¼ 3.42, 1H), 5.74 (s,
1H), 2.42–2.55 (t, 2H), 2.37–2.39 (t, 2H), 2.03–2.11 (m, 2H); IR (film):
n ¼ 3052, 2919, 1708, 1635, 1505, 865, 701; MS (70 eV) m=z (%): 212

Vinyl Sulfide Synthesis
2729
([M þ 1]þ , 6), 211 (Mþ , 34), 158 (84), 142 (100), 121 (46), 61 (28), 58
(72). Anal. calcd. for C9H9NOS2: C, 51.16; H, 4.29; found: C, 51.21;
H, 4.15.
3-(Pyrimidin-2-ylsulfanyl)-cyclohex-2-enone (3o): d ¼ 8.77–8.82 (m,
2H), 7.23–7.25 (m, 1H), 5.72 (s, 1H), 2.72–2.76 (t, 2H), 2.17–2.21 (t,
2H), 1.95–1.99 (m, 2H); IR (film): n ¼ 3055, 2978, 1713, 1652, 1506,
885, 775; MS (70 eV) m=z (%): 207 ([M þ 1]þ , 14), 206 (Mþ , 100), 154
(68), 137 (56), 111 (48), 58 (63), 15 (55). Anal. calcd. for C10H10N2OS:
C, 58.23; H, 4.89; found: C, 58.21; H, 4.85.
ACKNOWLEDGMENT
This work was funded by the Natural Science Foundation of Zhejiang
Province, PR China (Project Y407240).
REFERENCES
1. Sader, H. S.; Johnson, D. M.; Jones, R. N. In vitro activities of the novel
cephalosporin LB 11058 against multidrug-resistant staphylococci and Strep-
tococci. Antimicrob. Agents Chemother. 2004, 48, 53–62.
2. Johannesson, P.; Lindeberg, G.; Johansson, A.; Nikiforovich, G. V.; Gogoll,
A.; Synnergren, B.; Le Greves, M.; Byberg, F.; Karlen, A.; Hallberg, A. Vinyl
sulfide cyclized analogues of angiotensin II with high affinity and full agonist
activity at the AT 1 receptor. J. Med. Chem. 2002, 45, 1767–1777.
3. Lam, H. W.; Cooke, P. A.; Pattenden, G.; Bandaranayake, W. M.; Wickra-
masinghe, W. A. Structure and total synthesis of benzylthiocrellidone, a
novel dimedone-based vinyl sulfide from the sponge Crella spinulata. J.
Chem. Soc., Perkin Trans. 1 1999, 847–848.
4. Marcantoni, E.; Massaccesi, M.; Petrini, M.; Bartoli, G.; Bellucci, M. C.;
Bosco, M.; Sambri, L. A novel route to the vinyl sulfide of nine-membered
macrocycle moiety of griseoviridin. J. Org. Chem. 2000, 65, 4553–4559.
5. Morimoto, K.; Tsuji, K.; Iio, T.; Miyata, N.; Uchida, A.; Osawa, R.; Kitsu-
taka, H.; Takahashi, A. DNA damage in forestomach epithelium from male
F344 rats following oral administration of tert-butylquinone, one of the for-
estomach metabolites of 3-BHA. Carcinogenesis 1991, 12(4), 703–708.
6. Zyk, N. V.; Beloglazkina, E. K.; Belova, M. A.; Dubinina, N. S. Methods for
the synthesis of vinyl sulfides. Russ. Chem. Rev. 2003, 72(9), 769–786.
7. Kondo, T.; Mitsudo, T. For transition-metal-catalyzed carbon–sulfur bond
formations. Chem. Rev. 2000, 100, 3205–3220.
8. Benati, L.; Capella, L.; Montevecchi, P. C.; Spagnolo, P. Stereoselective for-
mation of conjugated enynes via coupling of alkynyliodonium tosylates and
the radical addition of benzenethiol to alkynes. J. Chem. Soc., Perkin Trans. 1
1995, 1035–1038.

2730
S.-R. Guo and Y.-Q. Yuan
9. Benati, L.; Montevecchi, P. C.; Spagnolo, P. Free-radical reactions of benze-
nethiol and diphenyl disulfide with alkynes: Chemical reactivity of intermedi-
ate 2-(phenylthio)vinyl radicals. J. Chem. Soc., Perkin Trans. 1 1991, 2103–
2108.
10. Aucagne, V.; Tatibouet, A.; Rollin, P. Wittig approach to carbohydrate-
derived vinyl sulfides, new substrates for regiocontrolled ring-closure reac-
tions. Tetrahedron 2004, 60, 1817–1826.
11. Stephan, E.; Olaru, A.; Jaouen, G. Synthesis of methyl vinyl sulfides: The role
of boron trifluoride in promoting a Horner–Wittig-type reaction. Tetra-
hedron Lett. 1999, 40, 8571–8574.
12. Sugoh, K.; Kuniyasu, H.; Sugae, T.; Ohtaka, A.; Takai, Y.; Tanaka, A.;
Machino, C.; Kambe, N.; Kurosawa, H. A prototype of transition-metal-
catalyzed carbothiolation of alkynes. J. Am. Chem. Soc. 2001, 123(21),
5108–5109.
13. Carpita, A.; Rossi, R.; Scamuzzi, B. Palladium-catalyzed reactions of trialk-
ystannyl phenyl sulfides with alkenyl bromides—A new diastereoselective
synthesis of (E)-1-alkenyl phenyl sulfides. Tetrahedron Lett. 1989, 30, 2699–
2702.
14. Cristau, H. J.; Chabaud, B.; Labaudiniere, R.; Christol, H. Synthesis of vinyl
selenides or sulfides and ketene selenoacetals or thioacetals by nickel (II):
Vinylation of sodium benzeneselenolate or benzenethiolate. J. Org. Chem.
1986, 51, 875–878.
15. Bates, G. G.; Michael, Q. P. S.; Venkataraman, D. Copper-catalyzed syn-
thesis of vinyl sulfides. Org. Lett. 2004, 26, 5005–5008.
16. Zhang, H.; Cai, Q.; Ma, D. Amino acid promoted CuI-catalyzed C-N bond
formation between aryl halides and amines or N-containing heterocycles. J.
Org. Chem. 2005, 70, 5164–5173.
17. Ma, D.; Cai, Q. N,N-Dimethyl glycine-promoted Ullmann coupling reaction
of phenols and aryl halides. Org. Lett. 2003, 21, 3799–3802.
18. Xie, X.; Cai, G.; Ma, D. CuI=L-proline-catalyzed coupling reactions of aryl
halides with activated methylene compounds. Org. Lett. 2005, 21, 4693–4695.
19. Wang, Z., Mo, H., Bao, W. Mild, efficient, and highly stereoselective syn-
thesis of (Z)-vinyl chalcogenides from vinyl bromides catalyzed by copper(I)
in ionic liquids based on amino acids. Synlett, 2007, 91–94.
20. Zheng, Y.; Du, X.; Bao, W. L-Proline promoted cross-coupling of vinyl
bromide with thiols catalyzed by CuBr in ionic liquid. Tetrahedron Lett.
2006, 47, 1217–1220.