Free radical reaction of sodium arenesulfinates with acetylenes: New regio- and stereoselective preparation of (E)-β-(phenylseleno)vinyl sulfones

Article abstract of DOI:10.1081/SCC-120003616

Free radical reaction of terminal acetylenes with sodium arenesulfinates and diphenyl diselenide in aqueous acetic acid affo31yrded high yields of the regio- and stereoselective (E)-β-(phenylseleno)vinyl sulfones.

Full text of DOI:10.1081/SCC-120003616

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FREE RADICAL REACTION OF SODIUM ARENESULFINATES
WITH ACETYLENES: NEW REGIO- AND STEREOSELECTIVE
PREPARATION OF (E)-β-(PHENYLSELENO)VINYL
SULFONES
Xian Huang a , Qing Xu a , Chun-Gen Liang a & Qi-Weng He a
a Department of Chemistry , Zhejiang University , Xixi Campus, Hangzhou, 310028, P.R.
China
Published online: 16 Aug 2006.
To cite this article: Xian Huang , Qing Xu , Chun-Gen Liang & Qi-Weng He (2002) FREE RADICAL REACTION OF SODIUM
ARENESULFINATES WITH ACETYLENES: NEW REGIO- AND STEREOSELECTIVE PREPARATION OF (E)-β-(PHENYLSELENO)VINYL
SULFONES, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
32:8, 1243-1249, DOI: 10.1081/SCC-120003616
To link to this article: http://dx.doi.org/10.1081/SCC-120003616
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SYNTHETIC COMMUNICATIONS, 32(8), 1243–1249 (2002)
FREE RADICAL REACTION OF SODIUM
ARENESULFINATES WITH ACETYLENES:
NEW REGIO- AND STEREOSELECTIVE
PREPARATION OF (E )-b-
(PHENYLSELENO)VINYL SULFONES
*
Xian Huang, Qing Xu, Chun-Gen Liang,
and Qi-Weng He
Department of Chemistry, Zhejiang University
(Xixi Campus), Hangzhou 310028, P.R. China
ABSTRACT
Free radical reaction of terminal acetylenes with sodium
arenesulfinates and diphenyl diselenide in aqueous acetic
acid afforded high yields of the regio- and stereoselective
(E )-b-(phenylseleno)vinyl sulfones.
Unsaturated sulfones and vinyl selenides are both known as reactive
compounds, and have found numerous synthetic applications in organic
chemistry.1,2 Preparation of selenovinyl sulfones and their utilization in
organic synthesis have been intensively studied in the past decades,3 and
have continued to attract much attention in organic chemistry in recent
years.4 It has been reported that highly reactive sulfonyl radicals could be
generated from the corresponding sodium arenesulfinates in aqueous acetic
*Corresponding author.
1243
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

1244
HUANG ET AL.
acid5 via the disproportionation reaction of the in situ formed arenesulfinic
acids.6 Besides, diaryl diselenides are known to be good free radical traps
toward carbon-centered radicals.7 In these regards, we aim to develop a
simple and one-pot method to prepare the versatile selenovinyl sulfones
by using sodium arenesulfinates and diaryl diselenides as free radical pre-
cursors and traps, respectively (Scheme 1).
Scheme 1.
We firstly examined the reaction of phenylacetylene with sodium
p-toluenesulfinate and diphenyl diselenide. In a sealed tubular reactor,
simple stirring of the reactants in aqueous acetic acid at 80ꢀC afforded
89% yield of the target compound (E )-2b (Table 1, Entry 2). Compound
2b was suggested to be of E-configuration, as was satisfactorily confirmed
by spectra data comparison with the known compound.3b Thus, the spectra
of (E )-2b are identical with those of the known one. For example, the chemical
shift of the olefinic proton of (E )-2b is almost, and therefore is consi-
dered as, the same as the reported, i.e., 6.16 and 6.15 ppm,3b respectively.
Table 1. Preparation of (E)-b-(Phenylseleno)vinyl Sulfones
Time
(h)
Yields*
(%)
Product
R
R1
2a
2b
2c
2d
2e
2f
2g
2h
2i
Ph
Ph
Ph
C5H11
C5H11
C6H13
C6H13
CH3OCH2
CH3OCH2
CH3OCH2
H
CH3
Cl
H
CH3
H
CH3
H
CH3
Cl
24
24
24
48
48
48
48
48
48
48
85
89
91
76
79
72
75
84
87
83
2j
*Isolated yields based on diphenyl diselenide.

SODIUM ARENESULFINATES AND ACETYLENES
1245
Other selenovinyl sulfones were obtained similarly in good to high
yields and their configurations were assigned by analogues rationalization
(Table 1). In all reactions, no significant amounts of the Z-isomers could be
isolated.
Effective inhibition of these reactions by the addition of hydroquinone
(1 equiv. mole), resulting in an extended period of reaction time, indicated
that a free radical mechanism was most probably involved in the reaction
process,5a and if this were the case, then these reactions might have pro-
ceeded via a free radical mechanism similar to the one proposed by Back
et al.3b Secondly, we have previously investigated the reaction of acetylenes
with sodium arenesulfinates and diaryl ditellurides, affording (E )-b-(aryltel-
luro)vinyl sulfones, and a free radical mechanism was also proposed.8 While
the only difference in these two reactions is the period of reaction time
needed, lied upon the reaction rates of diselenides or ditellurides toward
carbon radicals.7b Therefore, we may conclude that organic diselenides
and ditellurides played the same role as free radical traps in these reactions.
Furthermore, stereoselectivity in present reactions was also confirmed by the
chemical shifts of the olefinic protons, which appeared at a relatively higher
field compared with those of the Z-isomers.4d We therefore proposed a
plausible mechanism as shown in Scheme 2 to explain the regio- and stereo-
selective formation of the products.
Scheme 2.
Firstly, the in situ generated sulfonyl radicals added efficiently to the
acetylenes to form tri-substituted b-sulfonyl vinyl radicals 3. The found high

1246
HUANG ET AL.
regio- and stereoselectivity in the addition step indicated that the reaction
rate of 3 with diphenyl diselenides is much faster than its conversion to 4.3b,8
Observed higher reactivity of radicals 3(R¼Ph) from phenylacetylene is
probably because vinyl radicals bearing phenyl group at the a-position of
the radical center, which may form p-radicals, are more stable than usual
vinyl radicals 3 (R¼alkyl).9
Except the conventional free radical selenosulfonation of acetylenes3
using the well-known intermediate Se-phenyl selenosulfonate PhSeTs,10
other methods were seldom reported to prepare these versatile (E )-b-
(phenylseleno)vinyl sulfones. Therefore, the present reaction provided a
new convenient and efficient approach for the preparation of these com-
pounds. By comparison, the present reaction has many advantages over the
conventional methods. For instance, in this straightforward and water-
dependent reaction, selenosulfonate preparation and solvent drying can be
avoided. In this regard, the arenesulfinate/diselenide system is a more con-
venient alternative than selenosulfonates and can be used instead in most
cases.
EXPERIMENTAL SECTION
General procedure: In a sealed two-neck tubular reactor equipped with
a condenser, the mixture of diphenyl diselenide (156 mg, 0.5 mmol), sodium
arenesulfinate (5 mmol), and acetylene (1.3 mmol) in 80% AcOH/H2O (5 ml)
was stirred under N2 at 80ꢀC. After the reaction was completed (by mon-
itoring TLC), the mixture was quenched with ethyl acetate (30ml), and then
washed successively with saturated aqueous sodium bicarbonate and brine
and then dried over magnesium sulfate. After evaporation of the solvent the
residue was purified by flash-column chromatography on silica gel (n-
Hexane/EtOAc 10/1 for 2a ꢁ 2c, 30/1 for 2d ꢁ 2g, 5/1 for 2h ꢁ 2j) to
afford the products in high yields.
(E )-1-Phenyl-1-(phenylseleno)-2-(benzenesulfonyl)ethene (2a): Yield
339 mg, 85%; m.p. 104 ꢁ 106ꢀC; 1H NMR (500 MHz, CDCl3): d 7.60 ꢁ 7.58
(d, J ¼ 7.30Hz, 2H), 7.46 ꢁ 7.39 (m, 6H), 7.32 ꢁ 7.23 (m, 5H), 7.18 ꢁ 7.16 (d,
J ¼ 7.30 Hz, 2H), 6.17 (s, 1H); IR (KBr): 3058, 1607, 1575, 1471, 1443, 1322,
1284, 1143, 1082, 875, 797, 743 cmÀ1; MS (EI): m/z (relative intensity, %)
400 (5, Mþ), 259 (31), 243 (5), 157 (15), 141 (27), 125 (9), 105 (36), 77 (100);
Anal. Calcd for C20H16O2SSe: C, 60.15; H, 4.04. Found: C, 60.03; H, 3.99.
(E )-1-Phenyl-1-(phenylseleno)-2-( p-toluenesulfonyl)ethene (2b): Yield
368 mg, 89%; m.p. 146 ꢁ 148ꢀC (lit.3b m.p. 152ꢀC); H NMR (500 MHz,
1
CDCl3): d 7.59 ꢁ 7.57 (d, J ¼ 7.05 Hz, 2H), 7.46 ꢁ 7.37 (m, 3H), 7.34 ꢁ 7.24
(m, 5H), 7.20 ꢁ 7.17 (d, J ¼ 7.20Hz, 2H), 7.10 ꢁ 7.08 (d, J ¼ 8.00 Hz, 2H),

SODIUM ARENESULFINATES AND ACETYLENES
1247
6.16 (s, 1H), 2.36 (s, 3H); IR (KBr): 3050, 2875, 1613, 1578, 1486, 1440,
1325, 1284, 1142, 1085, 896, 783, 768 cmÀ1; MS (EI): m/z (relative intensity,
%) 414 (6, Mþ), 259 (31), 257 (191), 157 (15), 155 (48), 139 (14), 105 (19), 91
(100), 77 (20).
(E )-1-Phenyl-1-(phenylseleno)-2-( p-chlorobenzenesulfonyl)ethene (2c):
Yield 394 mg, 91%; m.p. 150 ꢁ 152ꢀC; 1H NMR (500 MHz, CDCl3): d
7.61 ꢁ 7.58 (d, J ¼ 7.14 Hz, 2H), 7.48 ꢁ 7.39 (m, 3H), 7.34 ꢁ 7.24 (m, 7H),
7.18 ꢁ 7.16 (d, J ¼ 7.44 Hz, 2H), 6.14 (s, 1H); IR (KBr): 3055, 1600, 1577,
1474, 1438, 1325, 1284, 1139, 1083, 878, 796, 743 cmÀ1; MS (EI): m/z
(relative intensity, %) 434 (17, Mþ), 277 (7), 259 (86), 176 (9), 159 (19),
157 (32), 111 (100), 105 (57), 77 (48); Anal. Calcd for C20H15ClO2SSe: C,
55.37; H, 3.49. Found: C, 55. 61; H, 3.54.
(E )-2-(Phenylseleno)-1-(benzenesulfonyl)heptene (2d): Yield 299 mg,
76%; m.p. 50–52ꢀC; 1H NMR (400 MHz, CDCl3): d 7.81–7.78 (d,
J ¼ 8.38 Hz, J ¼ 1.26 Hz, 2H), 7.60–7.35 (m, 8H), 5.85 (s, 1H), 2.86–2.82
(t, J ¼ 7.96 Hz, 2H), 1.59–1.54 (m, 2H), 1.32–1.27 (q, J ¼ 6.03 Hz, 4H),
0.90 ꢁ 0.86 (t, J ¼ 7.06 Hz, 3H); IR (KBr): 3062, 2952, 2864, 1560, 1437,
1318, 1144, 1084, 813, 737 cmÀ1; MS (EI): m/z (relative intensity, %) 394
(6, Mþ), 338 (14), 237 (15), 157 (18), 141 (11), 125 (28), 95 (100), 77 (74);
Anal. Calcd for C19H22O2SSe: C, 58.01; H, 5.64. Found: C, 58.32; H, 5.75.
(E )-2-(Phenylseleno)-1-( p-toluenesulfonyl)heptene (2e): Yield 322 mg,
79%; m.p. 52–54ꢀC; 1H NMR (400 MHz, CDCl3): d 7.68–7.66 (d,
J ¼ 8.28 Hz, 2H), 7.54–7.51 (dd, J ¼ 8.10Hz, J ¼ 1.30Hz, 2H), 7.45–7.23
(m, 6H), 5.86 (s, 1H), 2.84–2.80(t, J ¼ 7.96 Hz, 2H), 2.42 (s, 3H), 1.58–1.53
(m, 2H), 1.32–1.27 (m, 4H), 0.90 ꢁ 0.86 (t, J ¼ 7.00 Hz, 3H); IR (KBr): 3061,
2951, 2864, 1560, 1437, 1319, 1142, 1084, 822, 736 cmÀ1; MS (EI): m/z
(relative intensity, %) 408 (12, Mþ), 352 (15), 251 (29), 157 (64), 155 (29),
139 (41), 95 (100), 91 (80), 77 (23).
(E )-2-(Phenylseleno)-1-(benzenesulfonyl)octene (2f): Yield 293 mg,
72%; yellow oil; 1H NMR (500 MHz, CDCl3): d 7.80 ꢁ 7.78 (d, J ¼ 7.45 Hz,
2H), 7.60 ꢁ 7.48 (m, 5H), 7.45–7.35 (m, 3H), 5.85 (s, 1H), 2.86–2.82 (t,
J ¼ 7.92 Hz, 2H), 1.59–1.54 (m, 2H), 1.35–1.23 (m, 6H), 0.90 ꢁ 0.87 (t,
J ¼ 6.92 Hz, 3H); IR (film): 3083, 2942, 2877, 1576, 1438, 1317, 1145,
1085, 813, 742 cmÀ1; MS (EI): m/z (relative intensity, %) 408 (7, Mþ), 338
(22), 251 (14), 157 (16), 141 (14), 125 (37), 109 (100), 77 (75); exact mass
(Mþ) calcd for C20H24O2SSe 408.0662. Found 408.0676.
(E )-2-(Phenylseleno)-1-( p-toluenesulfonyl)octene (2g): Yield 316 g,
75%; yellow oil; 1H NMR (400 MHz, CDCl3): d 7.69 ꢁ 7.66 (d, J ¼ 8.24 Hz,
2H), 7.53–7.51 (dd, J ¼ 7.58 Hz, J ¼ 1.40Hz, 2H), 7.43–7.35 (m, 3H),
7.30–7.28 (d, J ¼ 8.08 Hz, 2H), 5.86 (s, 1H), 2.85–2.80 (t, J ¼ 7.94 Hz, 2H),
2.42 (s, 3H), 1.58–1.53 (m, 2H), 1.31–1.24 (m, 6H), 0.91 ꢁ 0.86 (t,
J ¼ 6.86 Hz, 3H); IR (film): 3057, 2925, 2850, 1570, 1446, 1317, 1147,

1248
HUANG ET AL.
1085, 808, 743 cmÀ1; MS (EI): m/z (relative intensity, %) 422 (10, Mþ), 352
(16), 265 (23), 157 (71), 155 (34), 139 (60), 109 (100), 91 (99); 77 (25); exact
mass (Mþ) calcd for C21H26O2SSe 422.0819. Found 422.0807.
(E )-1-Methoxy-2-(phenylseleno)-3-(benzenesulfonyl)propene (2h): Yield
308 mg, 84%; m.p. 78–80ꢀC; H NMR (400 MHz, CDCl3): d 7.78–7.75 (dd,
1
J ¼ 8.38 Hz, J ¼ 1.22 Hz, 2H), 7.63–7.38 (m, 8H), 5.65–5.63 (t, J ¼ 1.92 Hz,
1H), 4.81 (d, J ¼ 1.92 Hz, 2H), 3.44 (s, 3H); IR (KBr): 3061, 2931, 2822,
1559, 1445, 1369, 1304, 1270, 1146, 1083, 821, 737 cmÀ1; MS (EI): m/z
(relative intensity, %) 368 (5, Mþ), 211 (9), 157 (8), 141 (2), 125 (75), 77
(24), 69 (100), 57 (12), 45 (25); Anal. calcd for C16H16O3SSe: C, 52.32; H,
4.39. Found: C, 52.05; H, 4.28.
(E )-1-Methoxy-2-(phenylseleno)-3-( p-toluenesulfonyl)propene
(2i):
Yield 331 mg, 87%; m.p. 62–64ꢀC; 1H NMR (400 MHz, CDCl3): d 7.65–7.62
(d, J ¼ 8.24 Hz, 2H), 7.54–7.51 (dd, J ¼ 7.52 Hz, J ¼ 1.44 Hz, 2H),7.48–7.35
(m, 3H), 7.30–7.28 (d, J ¼ 8.00 Hz, 2H), 5.64 (t, J ¼ 1.84 Hz, 1H), 4.81–4.80
(d, J ¼ 1.84 Hz, 2H), 3.44 (s, 3H), 2.43 (s, 3H); IR (KBr): 3048, 2936, 2828,
1559, 1441, 1344, 1307, 1267, 1140, 1081, 819, 782, 745 cmÀ1; MS (EI): m/z
(relative intensity, %) 382 (7, Mþ), 225 (10), 157 (5), 155 (4), 139 (86), 91
(18), 69 (100), 57 (9), 45 (19).
(E )-1-Methoxy-2-(phenylseleno)-3-( p-chlorobenzenesulfonyl)propene
(2j): Yield 333 mg, 83%; m.p. 94–96ꢀC; 1H NMR (400 MHz, CDCl3): d
7.71–7.68 (d, J ¼ 8.56 Hz, 2H), 7.54–7.43 (m, 5H), 7.42–7.39 (d,
J ¼ 7.60Hz, 2H), 5.58 (t, J ¼ 1.84 Hz, 1H), 4.80(d, J ¼ 1.84 Hz, 2H), 3.46
(s, 3H); IR (KBr): 3067, 2927, 2825, 1577, 1475, 1361, 1312, 1271, 1141,
1088, 810, 742 cmÀ1; MS (EI): m/z (relative intensity, %) 402 (5, Mþ), 245
(8), 159 (47), 157 (9), 111 (14), 77 (12), 69 (100), 57 (15), 45 (21); Anal. calcd
for C16H15ClO3SSe: C, 47.83; H, 3.76. Found: C, 47.65; H, 3.69.
ACKNOWLEDGMENT
This work was supported by the Doctoral Program Foundation of
National Education Ministry of China and also by the Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences.
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Received in the UK January 21, 2001