A facile stereoselective synthesis of 1,3-dienyl sulfones via Stille coupling reactions of (E)-α-stannylvinyl sulfones with alkenyl iodides

Article abstract of DOI:10.1016/j.jorganchem.2006.11.014

Palladium-catalyzed hydrostannylation of acetylenic sulfones 1 in benzene at room temperature gives stereoselectively (E)-α-stannylvinyl sulfones 2 in good yields. (E)-α-Stannylvinyl sulfones 2 are new difunctional group reagents which undergo Stille coup

Full text of DOI:10.1016/j.jorganchem.2006.11.014

Journal of Organometallic Chemistry 692 (2007) 1125–1130
www.elsevier.com/locate/jorganchem
A facile stereoselective synthesis of 1,3-dienyl sulfones via Stille
coupling reactions of (E)-a-stannylvinyl sulfones with alkenyl iodides
*
Ming-Zhong Cai , Gui-Qin Chen, Wen-Yan Hao, Dong Wang
School of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi Province 330022, PR China
Received 28 September 2006; received in revised form 31 October 2006; accepted 7 November 2006
Available online 17 November 2006
Abstract
Palladium-catalyzed hydrostannylation of acetylenic sulfones 1 in benzene at room temperature gives stereoselectively (E)-a-stannyl-
vinyl sulfones 2 in good yields. (E)-a-Stannylvinyl sulfones 2 are new difunctional group reagents which undergo Stille coupling reactions
with alkenyl iodides 3 to afford stereoselectively 1,3-dienyl sulfones 4 in high yields.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Hydrostannylation; Acetylenic sulfone; (E)-a-Stannylvinyl sulfone; Stille coupling; 1,3-Dienyl sulfone; Stereoselective synthesis
1. Introduction
Diels–Alder reactions [8]. The stereoselective synthesis of
1,3-dienylsilanes [9], 1,3-dienyl sulfides [10], 1,3-dienyl sele-
nides [11], and 1,3-dienylstannanes [12] has already been
described in the literatures. 1,3-Dienyl sulfones are exten-
sively used as intermediates in organic synthesis [13] due
to the chemical versatility of the sulfone moiety. 1,3-Dienyl
sulfones are also excellent acceptors in Michael additions
[14] and 2p partners in cycloaddition reactions [15]. How-
ever, the stereocontrolled synthesis of 1,3-dienyl sulfones
has rarely aroused extensive attention [16]. The Stille cou-
pling reactions of vinylstannanes with alkenyl iodides
provides a convenient route to stereoselective synthesis of
1,3-dienes [17]. Allred and Liebeskind [18] reported that
a-(tributylstannyl)thiophene and alkenyl iodides were suc-
cessfully Stille-coupled to afford different products contain-
ing sulfur-substituted 1,3-diene structural skeleton. Herein,
we wish to report that 1,3-dienyl sulfones could be
conveniently synthesized by the palladium-catalyzed hyd-
rostannylation of acetylenic sulfones, followed by a Stille
coupling reaction with alkenyl iodides.
The stereocontrolled synthesis of conjugated dienes
attracts considerable interest in organic chemistry because
of their appearance in a wide variety of biologically active
molecules and their key synthetic intermediates [1]. The
synthesis of 1,3-dienes for use in the Diels–Alder reaction
is still an important challenge in organic synthesis [2]
although other elegant uses of these compounds have been
developed [3]. Conjugated dienes are usually prepared by
utilizing either a Wittig-type approach [4] or the transition
metal-catalyzed coupling reactions of stereodefined vinyl
halides with vinyl organometallic compounds [5]. Recently,
Whitby and co-workers [6] reported the insertion of 1-
lithio-1-halobutadiene into organozirconocenes providing
a stereocontrolled synthesis of (E,Z)-1,3-dienes.
The stereocontrolled synthesis of 1,3-dienes containing
metal or heteroatom functional groups is also of consider-
able interest in organic synthesis because many useful
functional group transformations can be achieved by intro-
duction and removal of metal or heteroatom functions [7].
Heteroatom-substituted 1,3-dienes are also useful precur-
sors to construct highly functionalized ring systems in
2. Results and discussion
Palladium-catalyzed hydrostannylation of alkynes
provides a simple general route for the synthesis of vinylst-
annanes [19]. Palladium-catalyzed hydrostannylation of
*
Corresponding author. Fax: +86 791 8120388.
E-mail address: caimzhong@163.com (M.-Z. Cai).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.11.014

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M.-Z. Cai et al. / Journal of Organometallic Chemistry 692 (2007) 1125–1130
R
H
SO2Ar
SnBu3
thioacetylenic compounds [20], alkynyl selenides [21], and
alkynyl sulfoxides [22] has been reported to be highly regio-
and stereoselective, providing a direct route for the stereo-
selective synthesis of 1,1-difunctional group reagents
containing heteroatom and tin. Recently, the palladium-
catalyzed hydrostannylation of propargylic sulfones has
also been described [23]. However, to the best of our knowl-
edge, no palladium-catalyzed hydrostannylation of acety-
lenic sulfones has been described so far. We investigated
the palladium-catalyzed hydrostannylation of acetylenic
sulfones in order to prepare (E)-a-stannylvinyl sulfones.
Our initial efforts were devoted to the selection of an effi-
cient catalyst and a suitable solvent for highly regio- and
stereoselective hydrostannylation reaction of acetylenic
sulfones 1 with Bu3SnH. Thus, 1-butyl-2-(phenylsulfo-
nyl)ethyne 1a (1 mmol) and Bu3SnH (1.05 mmol) were trea-
ted in THF or benzene (4 ml), at room temperature, with
Pd(0) and Pd(II) catalysts (Table 1). As shown in Table 1,
among the palladium catalysts tested [Pd(OAc)2,
PdCl2(PPh3)2, Pd(PPh3)4, and PdCl2], Pd(PPh3)4 proved
to be the most efficient. Both THF and benzene could be
used as the solvent, the use of benzene was the best choice.
Increasing the amount of Pd(PPh3)4 could shorten the reac-
tion time, but did not increase the yield of (E)-1-(tributyl-
stannyl)-1-(phenylsulfonyl)-1-hexene (2a). Taken together,
excellent result was obtained when the hydrostannylation
reaction was carried out with 1 mol% Pd(PPh3)4 in benzene
at room temperature for 4 h under an argon atmosphere.
To examine the scope for this hydrostannylation reac-
tion, the hydrostannylation reactions of a variety of acety-
lenic sulfones 1 with Bu3SnH were investigated under the
optimum conditions (Scheme 1), the experimental results
are summarized in Table 2. As shown in Table 2, the pal-
ladium-catalyzed hydrostannylation reactions of a variety
of acetylenic sulfones 1 with Bu3SnH proceeded smoothly
at room temperature in benzene giving the corresponding
(E)-a-stannylvinyl sulfones 2 in good to high yields. Inves-
tigations of the crude products 2 by 1H NMR spectroscopy
(400 MHz) showed their isomeric purities of more than
98%. One olefinic proton signal of compounds 2a, 2b, 2d,
and 2e splits characteristically into one triplet at d =
6.25–6.42 with coupling constant J = 4.8–7.2 Hz, which
Pd(PPh3)4 (1 mol %)
Benzene, rt
R
SO2Ar
+
Bu3SnH
1
2
Scheme 1.
Table 2
Synthesis of (E)-a-stannylvinyl sulfones 2a–ea
Entry
R
Ar
Product
Yieldb(%)
1
2
3
4
5
a
n-C4H9
n-C4H9
Ph
CH3OCH2
CH3OCH2
Ph
2a
2b
2c
2d
2e
90
88
82
83
80
4-CH3C6H4
Ph
Ph
4-CH3C6H4
Reactions were performed in the presence of 1 (1 mmol), Bu3SnH
(1.05 mmol), Pd(PPh3)4 (0.01 mmol), using benzene (4 ml) as solvent, at
room temperature for 4 h under Ar.
b
Isolated yield based on the 1 used.
indicated that the hydrostannylation to the acetylenic sulf-
ones had taken place with strong preference for the addi-
tion of the tin atom at the carbon adjacent to the
sulfonyl group. The stereochemistry of the addition was
1
readily apparent from the H NMR spectra of compounds
2 which showed a (3JSn117–H) coupling constant of 48–
52 Hz, fully in accord with an E geometry and overall cis
addition of tin hydride [24].
(E)-a-Stannylvinyl sulfones 2 are new difunctional
group reagents in which two synthetically versatile groups
are linked to the same olefinic carbon atom and can be con-
sidered both as vinylstannanes and as vinyl sulfones. With
a convenient route to the (E)-a-stannylvinyl sulfones 2, we
decided to establish the feasibility of using 2 in Stille cou-
pling reactions with alkenyl iodides 3. We observed that,
when the coupling reactions of 2 with a variety of alkenyl
iodides 3 were performed in DMF at room temperature
using Pd(PPh3)4 and CuI as co-catalyst (Scheme 2), fairly
rapid reactions occurred affording stereoselectively the
desired coupling products 4 in high yields. The experimen-
tal results are summarized in Table 3. The coupling reac-
tion of 2 with alkenyl bromides was very slow under the
same reaction conditions, only traces of coupling products
were obtained after 24 h of reaction time. The coupling
reaction of 2 with alkenyl chlorides did not occur at all.
It is well documented that the cross-coupling reaction
(Stille coupling) of vinylstannanes with organic halides in
the presence of a palladium catalyst occurs with retention
of configuration [25]. The E-configuration of the com-
Table 1
Catalytic activity of several palladium complexes and effect of solventsa
Entry Catalyst (mol%)
Solvent
Time (h) Isolated yield 2a (%)
1
2
3
4
5
6
7
8
9
Pd(OAc)2 (1)
Pd(OAc)2 (1)
PdCl2(PPh3)2 (1) THF
THF
Benzene 24
24
0
0
1
pounds 4a–i, and 4l–n has been proved by their H NMR
6
6
4
4
2
51
63
71
90
89
0
PdCl2(PPh3)2 (1) Benzene
Pd(PPh3)4 (1)
Pd(PPh3)4 (1)
Pd(PPh3)4 (5)
PdCl2 (1)
THF
Benzene
Benzene
THF
R
H
SO2Ar
R
H
SO2Ar
SnBu3
H
I
H
Pd(PPh3)4/CuI
DMF, r.t., 5-7 h
+
24
R1
R1
H
H
PdCl2(1)
Benzene 24
0
2
4
3
a
Reactions were performed with 1a (1 mmol), Bu3SnH (1.05 mmol),
solvent (4 ml) at room temperature under Ar.
Scheme 2.

M.-Z. Cai et al. / Journal of Organometallic Chemistry 692 (2007) 1125–1130
1127
Table 3
Synthesis of 1,3-dienyl sulfones 4a–n
Entry
R
Ar
R1
Product
Yielda(%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
a
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
Ph
4-CH3C6H4
Ph
4-CH3C6H4
4-CH3C6H4
Ph
Ph
Ph
Ph
n-C4H9
Ph
Ph
CH3OCH2
CH3OCH2
CH3OCH2
Ph
n-C4H9
CH3OCH2
Ph
4a
4b
4c
4d
4e
4f
85
90
87
82
83
81
88
91
84
86
87
86
88
85
Ph
Ph
4g
4h
4i
CH3OCH2
CH3OCH2
CH3OCH2
CH3OCH2
CH3OCH2
n-C4H9
Ph
Ph
4j
4-CH3C6H4
4-CH3C6H4
Ph
Ph
4k
4l
n-C4H9
n-C4H9
n-C4H9
4m
4n
Ph
Isolated yield based on the (E)-a-stannylvinyl sulfone 2 used.
spectra which show a doublet at d = 6.02–7.17 with a cou-
pling constant of 15.2–16.2 Hz, and this is also the evidence
of the retention of the E-configuration of the starting com-
pounds 3. In addition, the Z-configuration of the com-
3.1. General procedure for the synthesis of (E)-a-
stannylvinyl sulfones 2a–e
A 25 ml, two-necked, round-bottom flask equipped with
a magnetic stirring bar, and argon was charged sequentially
with acetylenic sulfone 1 (1 mmol), benzene (4 ml),
Pd(PPh3)4 (0.01 mmol) and Bu3SnH (1.05 mmol). The mix-
ture was stirred at room temperature for 4 h. After removal
of the solvent under reduced pressure, the residue was
diluted with light petroleum ether (20 ml) and filtered to
remove the palladium catalyst. The resulting solution was
concentrated under vacuum and the residue was purified
by flash chromatography on silica gel (eluent: light petro-
leum ether/Et2O, 7:1).
1
pound 4d was confirmed by the NOESY in the H NMR
spectrum. An enhancement of the allylic protons was
observed as the vinylic proton (d = 6.28) of 4d was irradi-
ated. There was no correlation between the vinylic proton
(d = 6.28) and aromatic proton. The correlation between
the vinylic proton (d = 6.28) and another vinylic proton
(d = 6.40) was also observed. The NOE results indicate
that 4d has the expected Z-configuration and the cross-cou-
pling reaction of (E)-a-stannylvinyl sulfones with alkenyl
iodides occurs with the configuration retention of both
the starting compounds 2 and the compounds 3.
In summary, a convenient synthetic method for 1,3-die-
nyl sulfones has been developed by the palladium-catalyzed
hydrostannylation of acetylenic sulfones, followed by a
Stille coupling reaction with alkenyl iodides. The present
method has the advantages of readily available starting
materials, straightforward and simple procedures, mild
reaction conditions, high stereoselectivity and high yields.
Investigations into the synthetic applications of 1,3-dienyl
sulfones 4 are currently in progress.
3.1.1. (E)-1-Phenylsulfonyl-1-tributylstannyl-1-hexene (2a)
IR (film): m (cmÀ1) 3066, 2958, 2927, 1713, 1587, 1446,
1285, 1138, 1082, 822, 689; 1H NMR (CDCl3): d 7.86–7.84
3
(m, 2H), 7.56–7.48 (m, 3H), 6.28 (t, J = 7.2 Hz, JSn117–H
= 52 Hz, 1H), 2.40–2.36 (m, 2H), 1.56–1.48 (m, 6H), 1.38–
1.29 (m, 6H), 1.22–1.15 (m, 4H), 1.11–1.06 (m, 6H), 0.90 (t,
J = 7.2 Hz, 9H), 0.80 (t, J = 7.2 Hz, 3H); 13C NMR
(CDCl3): d 157.4, 149.0, 143.5, 132.5, 128.8, 127.1, 31.0,
30.6, 28.8, 27.3, 22.3, 13.8, 13.7, 11.4; MS: m/z 513 (M+,
1.2), 457 (16), 291 (11), 197 (18), 111 (27), 73 (100). Anal.
Calc. for C24H42SO2Sn: C, 56.19; H, 8.19. Found: C,
55.89; H, 8.02%.
3. Experimental
1H NMR spectra were recorded on a Bruker AC-P400
(400 MHz) spectrometer with TMS as an internal standard
using CDCl3 as the solvent. 13C NMR (100 MHz) spectra
were recorded on a Bruker AC-P400 (400 MHz) spectrom-
eter using CDCl3 as the solvent. IR spectra were determined
on an FTS-185 instrument as neat films. Mass spectra were
obtained on a Finigan 8239 mass spectrometer. Microanal-
yses were measured using a Yanaco MT-3 CHN micro-
elemental analyzer. All reactions were carried out in
pre-dried glassware (150 °C, 4 h) and cooled under a stream
of dry Ar. Benzene was distilled from sodium prior to use.
DMF was dried by distillation over calcium hydride.
3.1.2. (E)-1-(4-Methylphenyl)sulfonyl-1-tributylstannyl-1-
hexene (2b)
IR (film): m (cmÀ1) 2957, 2926, 1588, 1456, 1285, 1138,
1
1082, 812, 665; H NMR (CDCl3): d 7.73 (d, J = 8.4 Hz,
2H), 7.29 (d, J = 8.4 Hz, 2H), 6.25 (t, J = 7.2 Hz,
3JSn117–H = 52 Hz, 1H), 2.42 (s, 3H), 2.41–2.34 (m, 2H),
1.57–1.49 (m, 6H), 1.36–1.30 (m, 6H), 1.22–1.16 (m, 4H),
1.10–1.05 (m, 6H), 0.91 (t, J = 7.2 Hz, 9H), 0.81 (t,
J = 7.2 Hz, 3H); 13C NMR (CDCl3): d 156.9, 149.3, 143.2,
140.6, 129.4, 127.2, 30.9, 30.7, 28.8, 27.3, 22.3, 21.5, 13.8,
13.7, 11.4; MS: m/z 527 (M+, 1.4), 471 (100), 469 (71), 213

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M.-Z. Cai et al. / Journal of Organometallic Chemistry 692 (2007) 1125–1130
(22), 211 (33), 209 (24), 91 (18). Anal. Calc. for
C25H44SO2Sn: C, 56.98; H, 8.35. Found: C, 56.75; H, 8.09%.
3.2.1. (5Z,7E)-6-(4-Methylphenyl)sulfonyl-5,7-
dodecadiene (4a)
IR (film): m (cmÀ1) 3030, 2957, 2928, 1715, 1620, 1598,
1
3.1.3. (E)-1-Phenylsulfonyl-1-tributylstannyl-2-
phenylethene (2c)
1457, 1321, 1155, 1086, 966, 813, 678; H NMR (CDCl3):
d 7.73 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 6.16
(t, J = 7.6 Hz, 1H), 6.14 (d, J = 15.2 Hz, 1H), 5.77 (dt,
J = 15.2, 7.6 Hz, 1H), 2.69–2.61 (m, 2H), 2.42 (s, 3H),
2.09–2.02 (m, 2H), 1.39–1.22 (m, 8H), 0.92–0.85 (m, 6H);
13C NMR (CDCl3): d 143.9, 141.8, 140.2, 138.7, 136.3,
129.5, 127.4, 124.5, 32.5, 31.4, 31.0, 28.3, 22.4, 22.1, 21.6,
13.9; MS: m/z 320 (M+, 2.4), 91 (34), 79 (43), 67 (97), 55
(82), 41 (100). Anal. Calc. for C19H28SO2: C, 71.25; H,
8.74. Found: C, 71.03; H, 8.62%.
IR (film): m (cmÀ1) 3063, 2957, 2921, 1585, 1446, 1286,
1
1136, 1081, 878, 745; H NMR (CDCl3): d 7.39 (d, J =
8.0 Hz, 2H), 7.27–7.09 (m, 9H), 1.67–1.61 (m, 6H), 1.43–
1.37 (m, 6H), 1.27–1.22 (m, 6H), 0.95 (t, J = 7.2 Hz, 9H);
13C NMR (CDCl3): d 154.4, 149.7, 141.4, 135.3, 131.9,
128.9, 128.2, 127.9, 127.7, 127.4, 29.0, 27.3, 13.7, 11.9;
MS: m/z 533 (M+, 1.1), 477 (100), 475 (71), 199 (17), 197
(35), 195 (24), 102 (21). Anal. Calc. for C26H38SO2Sn: C,
58.59; H, 7.13. Found: C, 58.32; H, 6.94%.
3.2.2. (1E,3Z)-1-Phenyl-3-phenylsulfonyl-1,3-octadiene
(4b)
3.1.4. (E)-1-Phenylsulfonyl-1-tributylstannyl-3-
methoxypropene (2d)
IR (film): m (cmÀ1) 3060, 2958, 2929, 1716, 1623, 1585,
1494, 1447, 1305, 1153, 1085, 963, 731, 689; 1H NMR
(CDCl3): d 7.89 (d, J = 8.0 Hz, 2H), 7.59–7.26 (m, 8H),
6.93 (d, J = 16.0 Hz, 1H), 6.69 (d, J = 16.0 Hz, 1H), 6.43
(t, J = 8.0 Hz, 1H), 2.76–2.70 (m, 2H), 1.46–1.32 (m, 4H),
0.91 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3): d 143.1,
141.6, 140.1, 136.3, 133.2, 132.9, 129.1, 128.7, 128.4,
127.2, 126.9, 123.0, 31.4, 28.7, 22.4, 13.9; MS: m/z 326
(M+, 2.7), 185 (9), 155 (13), 143 (17), 129 (34), 77 (28),
57 (35), 41 (100). Anal. Calc. for C20H22SO2: C, 73.62;
H, 6.74. Found: C, 73.35; H, 6.53%.
IR (film): m (cmÀ1) 2958, 2926, 1712, 1597, 1455, 1285,
1
1138, 1083, 830, 667; H NMR (CDCl3): d 7.86–7.83 (m,
3
2H), 7.60–7.53 (m, 3H), 6.42 (t, J = 4.8 Hz, JSn117–H
= 48 Hz, 1H), 4.39 (d, J = 4.8 Hz, 2H), 3.30 (s, 3H),
1.48–1.41 (m, 6H), 1.32–1.26 (m, 6H), 1.05–1.00 (m, 6H),
0.88 (t, J = 7.2 Hz, 9H); 13C NMR (CDCl3): d 153.8,
148.4, 142.3, 133.0, 129.0, 127.0, 70.7, 58.5, 28.7, 27.2,
13.7, 11.3; MS: m/z 501 (M+, 1.7), 445 (100), 443 (72),
441 (34), 197 (27), 195 (21), 41 (22). Anal. Calc. for
C22H38SO3Sn: C, 52.74; H, 7.58. Found: C, 52.48; H,
7.41%.
3.2.3. (1E,3Z)-1-Phenyl-3-(4-methylphenyl)sulfonyl-1,3-
octadiene (4c)
3.1.5. (E)-1-(4-Methylphenyl)sulfonyl-1-tributylstannyl-3-
methoxypropene (2e)
IR (film): m (cmÀ1) 3059, 2957, 2928, 1714, 1622, 1597,
1495, 1449, 1291, 1151, 1086, 963, 813, 693; 1H NMR
(CDCl3): d 7.77 (d, J = 8.0 Hz, 2H), 7.41–7.26 (m, 7H),
6.93 (d, J = 15.6 Hz, 1H), 6.68 (d, J = 15.6 Hz, 1H), 6.40
(t, J = 7.6 Hz, 1H), 2.76–2.70 (m, 2H), 2.41 (s, 3H), 1.46–
1.33 (m, 4H), 0.92 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3):
d 144.2, 142.7, 140.3, 138.7, 136.4, 132.8, 129.7, 128.7,
128.4, 127.3, 126.9, 123.1, 31.4, 28.7, 22.5, 21.6, 13.9;
MS: m/z 340 (M+, 3.8), 185 (14), 155 (21), 143 (27), 129
(63), 91 (100). Anal. Calc. for C21H24SO2: C, 74.12; H,
7.05. Found: C, 73.87; H, 7.08%.
IR (film): m (cmÀ1) 2959, 2925, 1713, 1598, 1456, 1285,
1138, 1085, 831, 809; 1H NMR (CDCl3): d 7.72 (d,
J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.39 (t,
3
J = 4.8 Hz, JSn117–H = 48 Hz, 1H), 4.39 (d, J = 4.8 Hz,
2H), 3.30 (s, 3H), 2.43 (s, 3H), 1.47–1.42 (m, 6H), 1.32–
1.26 (m, 6H), 1.04–1.00 (m, 6H), 0.88 (t, J = 7.2 Hz, 9H);
13C NMR (CDCl3): d 153.3, 148.7, 143.8, 139.4, 129.6,
127.1, 70.7, 58.5, 28.7, 27.2, 21.6, 13.6, 11.3; MS: m/z 515
(M+, 1.4), 459 (100), 457 (86), 455 (44), 211 (25), 209
(17), 91 (8). Anal. Calc. for C23H40SO3Sn: C, 53.64; H,
7.77. Found: C, 53.43; H, 7.52%.
3.2.4. (2E,4Z)-1-Methoxy-4-(4-methylphenyl)sulfonyl-2,4-
nonadiene (4d)
3.2. General procedure for the synthesis of 1,3-dienyl
sulfones 4a–n
CH3
(E)-a-Stannylvinyl sulfone 2 (1.0 mmol) and alkenyl
iodide 3 (1.1 mmol) were dissolved in DMF (10 ml) under
Ar at room temperature. Pd(PPh3)4 (0.05 mmol) and CuI
(0.75 mmol) were then added. The mixture was stirred for
5–7 h at room temperature and monitored by TLC (SiO2)
for the disappearance of the starting (E)-a-stannylvinyl sul-
fone 2. The reaction mixture was diluted with diethyl ether
(30 ml), filtered and then treated with 20% aqueous KF
(10 ml) for 30 min before being dried and concentrated.
The residue was purified by column chromatography on
silica gel (eluent: light petroleum ether/Et2O, 5:1).
Observed NOESY Correlations
H
CH3(CH2)2CH2
SO2
Hvinyl / CH2(allylic)
CH2(allylic) / CH(aromatic)
Hvinyl / Hvinyl
H
H
H
CH2OCH3
4d
IR (film): m (cmÀ1) 2927, 2872, 1720, 1620, 1597, 1494,
1
1455, 1302, 1153, 1086, 966, 814, 679; H NMR (CDCl3):
d 7.73 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 6.40

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1129
(d, J = 15.8 Hz, 1H), 6.28 (t, J = 7.6 Hz, 1H), 5.92 (dt,
J = 15.8, 5.8 Hz, 1H), 3.94 (d, J = 5.6 Hz, 2H), 3.29 (s,
3H), 2.71–2.65 (m, 2H), 2.42 (s, 3H), 1.41–1.26 (m, 4H),
0.89 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3): d 144.1,
143.6, 139.5, 138.6, 130.7, 129.6, 127.3, 126.9, 72.4, 58.1,
31.3, 28.4, 22.4, 21.6, 13.8; MS: m/z 308 (M+, 1.1), 139
(16), 110 (100), 91 (37), 45 (23), 41 (14). Anal. Calc. for
C17H24SO3: C, 66.24; H, 7.79. Found: C, 66.13; H, 7.53%.
124.4, 32.7, 31.0, 22.2, 13.9; MS: m/z 326 (M+, 4.8), 184
(26), 155 (57), 128 (67), 115 (88), 91 (100), 77 (63), 41
(78). Anal. Calc. for C20H22SO2: C, 73.62; H, 6.74. Found:
C, 73.48; H, 6.49%.
3.2.9. (2Z,4E)-1,6-Dimethoxy-3-phenylsulfonyl-2,4-
hexadiene (4i)
IR (film): m (cmÀ1) 3064, 2929, 2824, 1721, 1628, 1584,
1447, 1306, 1153, 962, 734, 689; 1H NMR (CDCl3): d
7.86–7.84 (m, 2H), 7.63–7.52 (m, 3H), 6.40 (t, J = 5.2 Hz,
1H), 6.27 (d, J = 15.6 Hz, 1H), 6.02 (dt, J = 15.6, 5.6 Hz,
1H), 4.65 (d, J = 5.2 Hz, 2H), 3.92 (d, J = 5.2 Hz, 2H),
3.39 (s, 3H), 3.25 (s, 3H); 13C NMR (CDCl3): d 141.0,
140.3, 138.5, 133.7, 132.3, 129.2, 127.4, 124.8, 72.1, 69.5,
58.7, 58.1; MS: m/z 282 (M+, 2.8), 141 (29), 125 (61), 109
(79), 77 (67), 45 (100). Anal. Calc. for C14H18SO4: C,
59.58; H, 6.38. Found: C, 59.31; H, 6.20%.
3.2.5. (2E,4Z)-1-Methoxy-4-phenylsulfonyl-2,4-nonadiene
(4e)
IR (film): m (cmÀ1) 3065, 2957, 2929, 1717, 1618, 1584,
1
1447, 1306, 1155, 1086, 965, 728, 689; H NMR (CDCl3):
d 7.87–7.85 (m, 2H), 7.60–7.50 (m, 3H), 6.42 (d,
J = 15.6 Hz, 1H), 6.32 (t, J = 7.6 Hz, 1H), 5.93 (dt,
J = 15.6, 5.8 Hz, 1H), 3.94 (d, J = 5.6 Hz, 2H), 3.29 (s,
3H), 2.72–2.63 (m, 2H), 1.41–1.30 (m, 4H), 0.89 (t,
J = 7.2 Hz, 3H); 13C NMR (CDCl3): d 144.1, 141.5,
139.2, 133.2, 130.8, 129.1, 127.2, 126.7, 72.4, 58.1, 31.2,
28.5, 22.4, 13.9; MS: m/z 294 (M+, 1.2), 121 (24), 110
(100), 105 (29), 79 (53), 45 (27), 41 (30). Anal. Calc. for
C16H22SO3: C, 65.31; H, 7.48. Found: C, 65.14; H, 7.25%.
3.2.10. (1E,3Z)-1-Phenyl-3-phenylsulfonyl-5-methoxy-1,3-
pentadiene (4j)
IR (film): m (cmÀ1) 3062, 2941, 1613, 1582, 1447, 1369,
1
1302, 1151, 950, 740, 684; H NMR (CDCl3): d 7.88 (d,
J = 7.6 Hz, 2H), 7.63–7.50 (m, 3H), 7.38–7.26 (m, 5H),
6.79 (s, 2H), 6.52 (t, J = 5.2 Hz, 1H), 4.68 (d, J = 5.2 Hz,
2H), 3.42 (s, 3H); 13C NMR (CDCl3): d 140.5, 139.9,
139.5, 136.0, 134.3, 133.6, 129.2, 128.8, 128.7, 127.4, 126.9,
121.5, 69.6, 58.7; MS: m/z 314 (M+, 1.5), 157 (21), 141
(35), 129 (47), 115 (33), 77 (56), 45 (100). Anal. Calc. for
C18H18SO3: C, 68.80; H, 5.73. Found: C, 68.53; H, 5.64%.
3.2.6. (1Z,3E)-1-Phenyl-2-phenylsulfonyl-5-methoxy-1,3-
pentadiene (4f)
IR (film): m (cmÀ1) 3059, 2924, 2855, 1590, 1447, 1306,
1
1146, 1095, 970, 784, 744; H NMR (CDCl3): d 7.88 (d,
J = 8.0 Hz, 2H), 7.58–7.38 (m, 9H), 6.40 (dt, J = 16.2,
4.8 Hz, 1H), 6.29 (d, J = 16.2 Hz, 1H), 3.93 (d,
J = 4.4 Hz, 2H), 3.21 (s, 3H); 13C NMR (CDCl3): d
140.0, 138.3, 137.5, 136.0, 133.4, 133.1, 130.4, 129.9,
129.0, 128.7, 128.0, 120.2, 72.4, 58.1; MS: m/z 314 (M+,
1.5), 204 (24), 185 (29), 155 (29), 143 (47), 129 (100), 115
(54), 91 (84), 77 (26). Anal. Calc. for C18H18SO3: C,
68.80; H, 5.73. Found: C, 68.64; H, 5.50%.
3.2.11. (1E,3Z)-1-Phenyl-3-(4-methylphenyl)sulfonyl-5-
methoxy-1,3-pentadiene (4k)
IR (film): m (cmÀ1) 3061, 2927, 1611, 1596, 1448, 1369,
1
1303, 1151, 947, 813, 740, 694; H NMR (CDCl3): d 7.76
(d, J = 8.0 Hz, 2H), 7.38–7.26 (m, 7H), 6.79 (s, 2H), 6.49
(t, J = 5.2 Hz, 1H), 4.68 (d, J = 4.8 Hz, 2H), 3.42 (s, 3H),
2.42 (s, 3H); 13C NMR (CDCl3): d 144.7, 139.7, 139.4,
137.5, 136.0, 134.1, 129.9, 128.8, 128.7, 127.4, 126.9,
121.6, 69.7, 58.7, 21.7; MS: m/z 328 (M+, 3.3), 185 (15),
157 (25), 141 (73), 129 (100), 115 (56), 91 (87), 45 (66), 41
(25). Anal. Calc. for C19H20SO3: C, 69.52; H, 6.09. Found:
C, 69.31; H, 5.85%.
3.2.7. (1Z,3E)-1,4-Diphenyl-2-phenylsulfonyl-1,3-butadiene
(4g)
IR (film): m (cmÀ1) 3060, 3027, 1718, 1621, 1585, 1491,
1292, 1159, 1091, 964, 748, 687; 1H NMR (CDCl3): d
7.65 (d, J = 7.6 Hz, 2H), 7.47–7.24 (m, 14H), 7.17 (d,
J = 15.6 Hz, 1H), 6.94 (d, J = 15.6 Hz, 1H); 13C NMR
(CDCl3): d 142.1, 140.9, 136.8, 136.2, 134.4, 133.9, 133.0,
129.8, 128.9, 128.8, 128.7, 128.6, 127.8, 127.7, 127.1,
123.0; MS: m/z 346 (M+, 16), 205 (100), 77 (43). Anal.
Calc. for C22H18SO2: C, 76.30; H, 5.20. Found: C, 76.11;
H, 5.03%.
3.2.12. (2Z,4E)-1-Methoxy-3-(4-methylphenyl)sulfonyl-
2,4-nonadiene (4l)
IR (film): m (cmÀ1) 3030, 2927, 2873, 1718, 1640, 1598,
1
1494, 1454, 1302, 1152, 967, 814, 679; H NMR (CDCl3):
d 7.72 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 6.26
(t, J = 5.2 Hz, 1H), 6.02 (d, J = 15.4 Hz, 1H), 5.89 (dt,
J = 15.4, 6.8 Hz, 1H), 4.62 (d, J = 4.8 Hz, 2H), 3.39 (s,
3H), 2.44 (s, 3H), 2.07–2.01 (m, 2H), 1.31–1.16 (m, 4H),
0.84 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3): d 144.5,
139.6, 138.5, 137.8, 137.5, 129.7, 127.5, 123.1, 69.5, 58.6,
32.5, 30.8, 22.0, 21.7, 13.9; MS: m/z 308 (M+, 1.2), 153
(46), 123 (37), 109 (38), 91 (68), 79 (54), 45 (100), 41 (69).
Anal. Calc. for C17H24SO3: C, 66.24; H, 7.79. Found: C,
66.02; H, 7.66%.
3.2.8. (1Z,3E)-1-Phenyl-2-phenylsulfonyl-1,3-octadiene
(4h)
IR (film): m (cmÀ1) 3059, 2956, 2928, 1714, 1634, 1586,
1
1446, 1305, 1150, 1082, 966, 750, 688; H NMR (CDCl3):
d 7.62 (d, J = 7.6 Hz, 2H), 7.49–7.26 (m, 8H), 7.18 (s,
1H), 6.38 (d, J = 15.4 Hz, 1H), 6.08 (dt, J = 15.4, 7.2 Hz,
1H), 2.19–2.14 (m, 2H), 1.42–1.25 (m, 4H), 0.92 (t,
J = 7.6 Hz, 3H); 13C NMR (CDCl3): d 142.1, 140.8,
138.2, 136.3, 134.0, 132.9, 129.6, 128.5, 128.4, 127.7,

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3.2.13. (2Z,4E)-1-Methoxy-3-phenylsulfonyl-2,4-nonadiene
(4m)
IR (film): m (cmÀ1) 3066, 2930, 2873, 1713, 1640, 1585,
1447, 1306, 1152, 967, 734, 689; 1H NMR (CDCl3): d 7.85–
7.83 (m, 2H), 7.62–7.51 (m, 3H), 6.29 (t, J = 5.2 Hz, 1H),
6.02 (d, J = 15.2 Hz, 1H), 5.90 (dt, J = 15.2, 6.8 Hz, 1H),
4.63 (d, J = 4.8 Hz, 2H), 3.39 (s, 3H), 2.05–2.01 (m, 2H),
1.31–1.25 (m, 2H), 1.21–1.15 (m, 2H), 0.84 (t, J = 7.2 Hz,
3H); 13C NMR (CDCl3): d 140.4, 139.4, 139.0, 138.0,
133.5, 129.1, 127.5, 123.0, 69.5, 58.6, 32.5, 30.8, 22.0, 13.8;
MS: m/z 294 (M+, 1.7), 269 (100), 267 (71), 213 (64), 153
(63), 109 (65), 79 (81), 57 (68), 41 (98). Anal. Calc. for
C16H22SO3: C, 65.31; H, 7.48. Found: C, 65.09; H, 7.32%.
(c) P.A. Grieco, S.A. May, M.D. Kaufman, Tetrahedron Lett. 39
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737.
3.2.14. (5Z,7E)-6-Phenylsulfonyl-5,7-dodecadiene (4n)
IR (film): m (cmÀ1) 3065, 2957, 2928, 1714, 1620, 1585,
1446, 1305, 1156, 1086, 966, 728, 688; H NMR (CDCl3):
1
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d 7.85 (d, J = 7.6 Hz, 2H), 7.59–7.48 (m, 3H), 6.19 (t,
J = 7.6 Hz, 1H), 6.15 (d, J = 15.4 Hz, 1H), 5.79 (dt,
J = 15.4, 7.2 Hz, 1H), 2.70–2.64 (m, 2H), 2.09–2.03 (m,
2H), 1.41–1.22 (m, 8H), 0.94–0.86 (m, 6H); 13C NMR
(CDCl3): d 142.2, 141.6, 140.0, 136.5, 133.0, 128.9, 127.3,
124.4, 32.4, 31.4, 31.0, 28.4, 22.4, 22.1, 13.9; MS: m/z 306
(M+, 3.4), 294 (27), 183 (44), 122 (65), 95 (72), 77 (100).
Anal. Calc. for C18H26SO2: C, 70.59; H, 8.49. Found: C,
70.31; H, 8.37%.
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3571;
Acknowledgements
(d) R.F. de la Pradilla, M.V. Buergo, C. Montero, A. Viso,
Tetrahedron 62 (2006) 2684.
We thank the National Natural Science Foundation of
China (Project No. 20462002) and the Natural Science
Foundation of Jiangxi Province in China (0420015) for
financial support.
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