One-Pot Stereoselective Synthesis of (Z)-1,2-Disubstituted vinyl sulfones by hydrostannylation-stille tandem reaction of acetylenic sulfones

Article abstract of DOI:10.1080/00397910802531971

(Z)-1,2-Disubstituted vinyl sulfones can be stereoselectively synthesized in one pot under mild conditions, in good yields, by the palladium-catalyzed hydrostannylation of acetylenic sulfones with tributyltin hydride, followed by Stille coupling with aryl

Full text of DOI:10.1080/00397910802531971

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One-Pot Stereoselective
Synthesis of (Z)-1,2-
Disubstituted Vinyl Sulfones
by Hydrostannylation–Stille
Tandem Reaction of Acetylenic
Sulfones
Guiqin Chen a b , Yan Yu a & Mingzhong Cai a
a Department of Chemistry , Jiangxi Normal
University , Nanchang, China
b Jiangxi Institute of Analysis and Testing ,
Nanchang, China
Published online: 19 Mar 2009.
To cite this article: Guiqin Chen , Yan Yu & Mingzhong Cai (2009) One-
Pot Stereoselective Synthesis of (Z)-1,2-Disubstituted Vinyl Sulfones by
Hydrostannylation–Stille Tandem Reaction of Acetylenic Sulfones, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 39:8, 1478-1487, DOI: 10.1080/00397910802531971
To link to this article: http://dx.doi.org/10.1080/00397910802531971
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Synthetic Communications1, 39: 1478–1487, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802531971
One-Pot Stereoselective Synthesis of
(Z)-1,2-Disubstituted Vinyl Sulfones by
Hydrostannylation–Stille Tandem Reaction
of Acetylenic Sulfones
Guiqin Chen,1,2 Yan Yu,1 and Mingzhong Cai1
1Department of Chemistry, Jiangxi Normal University, Nanchang, China
2Jiangxi Institute of Analysis and Testing, Nanchang, China
Abstract: (Z)-1,2-Disubstituted vinyl sulfones can be stereoselectively synthesized
in one pot under mild conditions, in good yields, by the palladium-catalyzed
hydrostannylation of acetylenic sulfones with tributyltin hydride, followed by
Stille coupling with aryl iodides.
Keywords: Hydrostannylation, stereoselective synthesis, Stille coupling,
tandem reaction, vinyl sulfone
INTRODUCTION
The stereoselective synthesis of polysubstituted alkenes remains a challen-
ging problem in organic synthesis and is still being actively explored
because of the fact that many biologically active compounds have the
structural unit of polysubstituted alkenes.[1] Vinyl sulfones have served
as a class of compounds of proven value in organic synthesis because of
the reactivity offered by the sulfonyl functional group.[2–4] Thus, vinyl sul-
fones are excellent acceptors for Michael additions[5] and 2p partners in
cycloaddition reaction.[6] In addition, alkylative desulfonylation has also
provided a new strategy for stereospecific alkene synthesis.[7,8] A variety
of methods have been developed for their preparation, including those
Received August 2, 2008.
Address correspondence to Mingzhong Cai, Department of Chemistry, Jiangxi
Normal University, Nanchang 330022, China. E-mail: caimzhong@163.com
1478

(Z)-1,2-Disubstituted Vinyl Sulfones
1479
involving Horner–Emmons reactions of carbonyl compounds and sulfonyl
phosphoranes,[9] Peterson reactions,[10] b-elimination of selenosul-
phones,[11] and selenosulfonation of acetylene.[12] An alternative conver-
gent process involved the combination of a sulfone-stabilized carbanion
with a carbonyl compound. In this regard, Knoevenagel condensation[13]
and Horner–Wittig reaction[14] achieved great successes, and the (E)-vinyl
sulfone was the exclusive product, but the preparation of the starting mate-
rials (such as sulfonomethyl-phosphonates) could be both inconvenient
and time-consuming. In addition, protodesilylation of a-phenylsulfonyl
allyl silanes also provided an indirect approach to vinyl sulfones.[15]
The stereoselective synthesis of polysubstituted vinyl sulfones is also
of considerable interest in organic synthesis. Huang et al.[16] reported
the synthesis of stereodefined Z-polysubstituted vinyl sulfones by hydro-
zirconation of acetylenic sulfones. Recently, Xie et al.[17,18] reported that
polysubstituted vinyl sulfones could be synthesized by carbomagnesiation
of acetylenic sulfones. Considering the importance of polysubstituted
vinyl sulfones, it is still of interest to develop new routes for the synthesis
of polysubstituted vinyl sulfones. Herein, we report that (Z)-1,2-disubsti-
tuted vinyl sulfones can be stereoselectively synthesized in one pot under
mild conditions, in good yields, by the palladium-catalyzed hydrostanny-
lation of acetylenic sulfones, followed by Stille coupling with aryl iodides.
RESULTS AND DISCUSSION
Recently, we found that the palladium-catalyzed hydrostannylation of
acetylenic sulfones could proceed highly regio- and stereoselectively,
affording (E)-a-stannylvinyl sulfones in high yields.[19] (E)-a-Stannylvinyl
sulfones are new difunctional group reagents in which two synthetically
versatile groups are linked to the same olefinic carbon atom and can be
considered both as vinylstannanes and as vinyl sulfones. Vinylstannanes
can undergo the Stille coupling reaction with organic halides.[20–22] The
tandem reaction has recently been of interest for organic synthesis because
it offers a convenient and economical method by which to prepare target
organic molecules.[23,24] The palladium-catalyzed hydrostannylation of
alkynes and the Stille reaction are acknowledged as useful tools for con-
structing complex organic molecules. Considering the fact that both the
hydrostannylation and Stille reaction were catalyzed by Pd(PPh3)4, we
tried to combine the two reactions, in one pot, to stereoselectively prepare
(Z)-1,2-disubstituted vinyl sulfones (Scheme 1).
We found that hydrostannylation of acetylenic sulfones 1 with tribu-
tyltin hydride using 5 mol% Pd(PPh3)4 in benzene, followed by solvent
exchange (to dimethylformamide, DMF) and subsequent reaction with

1480
G. Chen, Y. Yu, and M. Cai
Scheme 1. Synthesis of (Z)-1,2-disubstituted vinyl sulfones.
aryl iodides and 75 mol% copper iodide, gave the (Z)-1,2-disubstituted
vinyl sulfones 3 in good yields. The typical results are summarized in
Table 1. As shown in Table 1, the tandem hydrostannylation–Stille reac-
tion of tributyltin hydride with a variety of acetylenic sulfones and aryl
iodides proceeded smoothly, under very mild conditions, to afford the
corresponding (Z)-1,2-disubstituted vinyl sulfones 3 stereoselectively.
The nature of the substituents in aryl iodides has no influence on the
Stille reaction. The Stille coupling reaction of the intermediates 2 with
heteroaryl iodides and 1-iodonaphthalene also proceeded smoothly to
give the corresponding coupled products in good yields (entries 7 and
8). However, when aryl bromides were used as the electrophiles, the Stille
coupling reaction of the intermediates 2 did not occur at all.
Investigations of the crude products 3 by 1HNMR spectroscopy
(400 MHz) showed their isomeric purities by more than 98%. One olefinic
proton signal of compounds 3a-c, 3e, 3f, 3 h, and 3j splits characteristi-
cally into one triplet at d ¼ 6.11–6.25 with coupling constant J ¼ 4.8–
7.6 Hz, which indicated that the hydrostannylation to acetylenic sulfones
had taken place with strong preference for the addition of the tin atom
at the carbon adjacent to the arylsulfonyl group. It is well documented
that the Stille coupling reaction of vinylstannanes with organic halides,
Table 1. Synthesis of (Z)-1,2-disubstituted vinyl sulfones 3a–j
Entry
R
Ar
Ar1
Product
Yielda (%)
1
2
3
4
5
6
7
8
9
10
n-C4H9
n-C4H9
MeOCH2
Ph
n-C4H9
n-C4H9
Ph
n-C4H9
Ph
n-C4H9
Ph
Ph
4-MeC6H4
Ph
4-MeC6H4
4-MeC6H4
Ph
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f
76
74
70
69
80
81
79
75
78
76
4-MeOCOC6H4
4-MeC6H4
Ph
4-ClC6H4
4-O2NC6H4
2-Thieny1
1-Naphthy1
3-NCC6H4
4-MeOC6H4
3g
3h
3i
4-MeC6H4
3j
aIsolated yield based on the aryl iodide used.

(Z)-1,2-Disubstituted Vinyl Sulfones
1481
Scheme 2. Synthesis of stereodefined trisubstituted alkenes.
in the presence of a palladium catalyst, occurs with retention of config-
uration.[20,25] In addition, the Z-configuration of compound 3f was con-
firmed by nuclear Overhauser effect spectroscopy (NOESY) experiments.
An enhancement of the allylic protons was observed as the vinylic proton
of 3f was irradiated. A correlation between the allylic protons and the
aromatic protons of (4-methylphenyl)sulfonyl group was observed. The
NOE results indicate that compound 3f has the expected Z-configuration
and that the cross-coupling reaction of (E)-a-stannylvinyl sulfones with
aryl iodides occurs with retention of configuration.
We have also carried out the cross-coupling reaction of compounds 3
with Grignard reagents in the presence of NiCl2(PPh3)2 in THF to afford
trisubstituted alkenes with high stereoselectivity in moderate yields
(Scheme 2).
EXPERIMENTAL
General
Benzene was distilled from sodium immediately prior to use. DMF was
dried by distillation over calcium hydride. IR spectra were obtained with
a Perkin-Elmer 683 instrument as neat films. 1H NMR spectra were
recorded with a Bruker AC-400 (400-MHz) spectrometer using CDCl3
as solvent. 13CNMR spectra were recorded with a Bruker AC-400
(100-MHz) spectrometer using CDCl3 as solvent. Mass spectra (EI) were
determined with a Finnigan 8230 mass spectrometer. Microanalyses
were measured with a Yanaco MT-3 CHN microelemental analyzer.
Pd(PPh3)4 was prepared according to a literature procedure.[26] Acetylenic
sulfones 1 were prepared by a literature method.[27]
General Procedure for the Synthesis of (Z)-1,2-Disubstituted Vinyl
Sulfones 3a–j
A 25-mL, two-necked, round-bottomed flask equipped with a magnetic
stirring bar under an argon atmosphere was charged sequentially with

1482
G. Chen, Y. Yu, and M. Cai
acetylenic sulfone 1 (1 mmol), benzene (4 mL), Pd(PPh3)4 (0.05 mmol), and
Bu3SnH (1.1 mmol). The mixture was stirred at room temperature for 4 h,
the solvent was removed under reduced pressure, and the residue was
dissolved in DMF (10mL). Aryl iodide (0.9 mmol) and CuI (0.7 mmol) were
added, and the mixture was stirred at room temperature for 8–12 h. The
reaction mixture was diluted with Et2O (30 mL), filtered, and then treated
with 20% aqueous potassium fluoride (KF) (10 mL) for 30 min before the
organic layer was dried (MgSO4) and concentrated. The residue was purified
by column chromatography on silica gel (petroleum ether–Et2O, 5:1).
Data
(Z)-1-Phenyl-1-phenylsulfonyl-1-hexene (3a)
Oil. IR (neat): n (cmꢀ1) 3061, 2958, 2928, 1628, 1585, 1490, 1446, 1306,
1153, 1086, 760; 1H NMR (400 MHz, CDCl3): d 7.65 (d, J ¼ 7.6 Hz,
2H), 7.54–7.37 (m, 3H), 7.28–7.17 (m, 5H), 6.18 (t, J ¼ 7.6 Hz, 1H),
2.91–2.85 (m, 2H), 1.49–1.35 (m, 4H), 0.94 (t, J ¼ 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3): d 147.1, 142.0, 141.1, 135.9, 133.0, 130.2,
128.7, 128.5, 128.0, 127.7, 31.5, 28.5, 22.4, 13.9; MS (EI): m=z 300
(Mþ, 100), 196 (28), 117 (47). Anal. calc. for C18H20SO2: C, 71.97; H,
6.71. Found: C, 72.23; H, 6.93%.
(Z)-1-(4-methoxycarbonylphenyl)-1-phenylsulfonyl-1-hexene (3b)
Oil. IR (neat): n (cmꢀ1) 3066, 2956, 2927, 1717, 1607 1584, 1446, 1275,
1154, 1103, 1086, 772; 1H NMR (400MHz, CDCl3): d 7.92–7.90 (m,
2H), 7.66–7.63 (m, 2H), 7.53–7.51 (m, 1H), 7.43–7.39 (m, 2H), 7.29–7.26
(m, 2H), 6.21 (t, J ¼ 7.6 Hz, 1H), 3.91 (s, 3H), 2.93–2.87 (m, 2H), 1.52–
1.38 (m, 4H), 0.95 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d
166.6, 147.8, 141.4, 140.8, 140.4, 133.3, 130.2, 130.1, 129.2, 128.9, 127.7,
52.2, 31.4, 28.5, 22.4, 13.9; MS (EI): m=z 359 (Mþ þ 1, 100), 358 (Mþ,
85), 217 (99), 115 (78); Anal. calc. for C20H22SO4: C, 67.02; H, 6.19. Found:
C, 66.84; H, 6.25%.
(Z)-1-(4-Methylphenyl)-1-(4-methylphenylsulfonyl)-3-methoxypropene
(3c)
Oil. IR (neat): n (cmꢀ1) 2957, 2925, 1643, 1595, 1510, 1314, 1148, 1112,
1
816, 696; H NMR (400 MHz, CDCl3): d 7.49 (d, J ¼ 8.4 Hz, 2H), 7.18
(d, J ¼ 8.0 Hz, 2H), 7.10 (d, J ¼ 8.4 Hz, 2H), 7.04 (d, J ¼ 8.0 Hz, 2H),

(Z)-1,2-Disubstituted Vinyl Sulfones
1483
6.25 (t, J ¼ 4.8 Hz, 1H), 4.77 (d, J ¼ 4.8 Hz, 2H), 3.43 (s, 3H), 2.38 (s, 3H),
2.31 (s, 3H); 13C NMR (100 MHz, CDCl3): d 144.3, 143.3, 141.2, 138.8,
137.1, 131.8, 129.7, 129.4, 128.8, 127.9, 69.8, 58.6, 21.6, 21.2; MS (EI):
m=z 316 (Mþ, 3.6), 269 (100), 267 (67), 91 (23). Anal. calc. for
C18H20SO3: C, 68.34; H, 6.37. Found: C, 68.15; H, 6.21%.
(Z)-1,2-Diphenyl-1-phenylsulfonylethene (3d)
White solid, mp 129–130ꢁC (lit.,[28] 131ꢁC). IR (KBr): n (cmꢀ1) 3063,
2958, 2923, 1623, 1578, 1495, 1304, 1145, 1085, 776; 1H NMR
(400 MHz, CDCl3): d 7.51–7.24 (m, 15H), 7.18 (s, 1H); 13C NMR
(100 MHz, CDCl3): d 144.1, 141.5, 140.3, 135.8, 133.7, 132.9, 129.9,
129.4, 128.8, 128.7, 128.4, 128.2, 128.1, 127.8; MS (EI): m=z 320 (Mþ,
56), 269 (23), 179 (100), 77 (31).
(Z)-1-(4-Chlorophenyl)-1-(4-methylphenylsulfonyl)-1-hexene (3e)
Oil. IR (neat): n (cmꢀ1) 2957, 2926, 1629, 1596, 1487, 1456, 1319, 1152,
1087, 684; 1H NMR (400 MHz, CDCl3): d 7.52 (d, J ¼ 8.4 Hz, 2H),
7.23–7.20 (m, 4H), 7.14–7.12 (m, 2H), 6.13 (t, J ¼ 7.6 Hz, 1H), 2.89–
2.84 (m, 2H), 2.39 (s, 3H), 1.48–1.32 (m, 4H), 0.94 (t, J ¼ 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d 147.2, 144.2, 141.2, 138.0, 134.7,
134.5, 131.5, 129.5, 128.2, 127.7, 31.5, 28.5, 22.4, 21.6, 13.9; MS (EI):
m=z 350 (Mþ, 37Cl, 21), 348 (Mþ, 35Cl, 45), 151 (100), 91 (48). Anal. calc.
for C19H21SO2Cl: C, 65.40; H, 6.07. Found: C, 65.13; H, 5.88%.
(Z)-1-(4-Methylphenylsulfonyl)-1-(4-nitrophenyl)-1-hexene (3f)
Oil. IR (neat): n (cmꢀ1) 3067, 2958, 2927, 1626, 1597, 1520, 1492, 1348,
1
1152, 1086, 814; H NMR (400MHz, CDCl3): d 8.12–8.10 (m, 2H), 7.53
(d, J ¼ 8.4 Hz, 2H), 7.41–7.38 (m, 2H), 7.23 (d, J ¼ 8.4 Hz, 2H), 6.22 (t,
J ¼ 7.6 Hz, 1H), 2.93–2.87 (m, 2H), 2.40 (s, 3H), 1.53–1.39 (m, 4H), 0.95
(t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 148.4, 147.8, 144.6,
142.6, 140.8, 137.6, 131.1, 129.7, 127.7, 123.2, 31.3, 28.6, 22.5, 21.6, 13.9;
MS (EI): m=z 359 (Mþ, 52), 269 (100), 267 (87), 91 (56). Anal. calc. for
C19H21NSO4: C, 63.49; H, 5.89. Found: C, 63.21; H, 5.74%.
(Z)-2-Phenyl-1-phenylsulfonyl-1-(2-thienyl)ethene (3g)
White solid, mp 78–79ꢁC. IR (KBr): n (cmꢀ1) 3110, 1582, 1330, 1148, 1079,
1
728; H NMR (400 MHz, CDCl3): d 7.61 (d, J¼ 8.0 Hz, 2H), 7.48–7.40

1484
G. Chen, Y. Yu, and M. Cai
(m, 4H), 7.35–7.30 (m, 7H), 7.00–6.97 (m, 1H); 13C NMR (100 MHz, CDCl3):
d 142.2, 140.4, 137.3, 136.1, 133.6, 133.1, 129.9, 129.4, 128.9, 128.6,
128.0, 127.9, 127.8, 127.2; MS (EI): m=z 326 (Mþ, 2.2), 185 (56), 77 (100).
Anal. calc. for C18H14S2O2: C, 66.23; H, 4.32. Found: C, 66.41; H, 4.55%.
(Z)-1-(1-Naphthyl)-1-phenylsulfonyl-1-hexene (3h)
Oil. IR (neat): n (cmꢀ1) 3061, 2956, 2920, 1630, 1506, 1447, 1306, 1151, 1085,
803; 1H NMR (400 MHz, CDCl3): d 7.80–7.60 (m, 5H), 7.44–7.18 (m, 7H),
6.24 (t, J¼ 7.6 Hz, 1H), 2.93–2.86 (m, 2H), 1.47–1.32 (m, 4H), 0.95 (t, J ¼
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 148.2, 140.4, 140.3, 133.4, 133.
1, 132.9, 132.7, 129.3, 129.1, 128.6, 128.2, 128.1, 126.4, 125.9, 125.5, 124.7, 31.
4, 28.6, 22.5, 14.0; MS (EI): m=z 350 (Mþ, 1.2), 209 (92), 139 (93), 91 (100).
Anal. calc. for C22H22SO2: C, 75.39; H, 6.33. Found: C, 75.13; H, 6.44%.
(Z)-1-(3-Cyanophenyl)-2-phenyl-1-phenylsulfonylethene (3i)
White solid, mp 85–86ꢁC. IR (KBr): n (cmꢀ1) 3065, 2227, 1625, 1597,
1
1304, 1146, 1083, 749, 685; H NMR (400 MHz, CDCl3): d 7.71–7.63
(m, 3H), 7.49–7.44 (m, 6H), 7.38–7.28 (m, 5H), 7.20 (s, 1H); 13C NMR
(100 MHz, CDCl3): d 143.0, 142.4, 139.7, 137.2, 134.4, 133.4, 133.3,
132.9, 132.3, 129.4, 129.3, 129.2, 128.7, 128.1, 128.0, 118.1, 112.7; MS
(EI): m=z 345 (Mþ, 17), 203 (100), 91 (26). Anal. calc. for C21H15NSO2:
C, 73.02; H, 4.38. Found: C, 72.75; H, 4.21%.
(Z)-1-(4-Methoxyphenyl)-1-(4-methylphenylsulfonyl)-1-hexene (3j)
Oil. IR (neat): n (cmꢀ1) 2957, 2926, 1606, 1575, 1509, 1464, 1316, 1178,
1150, 688; 1H NMR (400 MHz, CDCl3): d 7.53 (d, J ¼ 8.0 Hz, 2H),
7.19 (d, J ¼ 8.0 Hz, 2H), 7.13–7.11 (m, 2H), 6.78–6.76 (m, 2H), 6.11 (t,
J ¼ 7.6 Hz, 1H), 3.79 (s, 3H), 2.86–2.82 (m, 2H), 2.38 (s, 3H), 1.47–1.32
(m, 4H), 0.93 (t, J ¼ 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 159.7,
146.4, 143.8, 141.6, 138.3, 131.5, 129.4, 128.3, 127.7, 113.3, 55.3, 31.6,
28.5, 22.4, 21.6, 14.0; MS (EI): m=z 344 (Mþ, 1.4), 209 (46), 178 (50),
165 (100), 91 (38). Anal. calc. for C20H24SO3: C, 69.74; H, 7.02. Found:
C, 69.51; H, 6.80%.
General Procedure for the Synthesis of Stereodefined Trisubstituted
Alkenes 5a–b
To a stirred suspension of NiCl2(PPh3)2 (0.05 mmol) and the (Z)-1,2-dis-
ubstituted vinyl sulfone 3 (1 mmol) in THF (6 mL), a 3.0 M THF solution

(Z)-1,2-Disubstituted Vinyl Sulfones
1485
of MeMgBr (15 mmol) was added at room temperature under Ar. The
mixture was stirred at reflux temperature for 48 h. After being cooled
to room temperature, the mixture was quenched with sat. aq. NH4Cl
(15 mL) and extracted with Et2O (2 ꢂ 30 mL). The organic layer was
washed with water (3 ꢂ 10 mL) and dried (MgSO4). Removal of the sol-
vent under reduced pressure gave an oil, which was purified by column
chromatography on silica gel using light petroleum ether as eluent.
Data
(E)-2-phenylhept-2-ene[29] (5a)
1
Oil. IR (neat): n (cmꢀ1) 3021, 2957, 2928, 1646, 1597, 851, 753; H NMR
(400 MHz, CDCl3): d 7.37–7.10 (m, 5H), 5.71 (t, J ¼ 6.4 Hz, 1H),
2.24–2.05 (m, 2H), 2.02 (s, 3H), 1.47–1.21 (m, 4H), 0.89 (t, J ¼ 7.2 Hz,
3H). Anal. calc. for C13H18: C, 89.59; H, 10.41. Found: C, 89.31; H, 10.29%.
(E)-1-Methyl-1,2-diphenylethene[29] (5b)
Oil. IR (neat): n (cmꢀ1) 3057, 2925, 1651, 1528, 1422; 1H NMR (400MHz,
CDCl3): d 7.52–7.03 (m, 10H), 6.71 (m, 1H), 2.15 (d, J ¼ 1.3 Hz, 3H). Anal.
calc. for C15H14: C, 92.74; H, 7.26. Found: C, 92.52; H, 7.03%.
CONCLUSION
In conclusion, we have developed an efficient and stereoselective one-pot
method for the synthesis of (Z)-1,2-disubstituted vinyl sulfones. The present
method has the advantages of readily available starting materials, straight-
forward and simple procedures, mild reaction conditions, and good yields.
ACKNOWLEDGMENT
We thank the Natural Science Foundation of Jiangxi Province in China
(2007GZW0172) for financial support.
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