Synthesis and reactivity of β-sulfonylvinylselenonium salts: A simple stereoselective synthesis of β-functionalized (Z)-vinyl sulfones

Article abstract of DOI:10.1039/b007715l

The treatment of alkynylsetenonium salt with benzenesulfinic acid in ⁱprOH gives (Z)-β-sulfonylvinylselenonium salts in good yields. The alkenylselenonium salts thus prepared react with nucleophiles such as alkoxides, halides, and acetylides to produce β-functionalized (Z)-vinyl sulfones in high yields. Furthermore, we succeeded in the simple stereoselective one-step synthesis of various chiral (Z)-β-alkoxyvinyl sulfones by the use of chiral alcohols.

Full text of DOI:10.1039/b007715l

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Synthesis and reactivity of ꢀ-sulfonylvinylselenonium salts:
a simple stereoselective synthesis of ꢀ-functionalized (Z)-vinyl
sulfones
1
Shin-ichi Watanabe,a Keiichirou Yamamoto,a Yukiko Itagaki,a Tatsunori Iwamura,a
Tetsuo Iwama,a Tadashi Kataoka,*a Genzoh Tanabeb and Osamu Muraokab
a Gifu Pharmaceutical University, 6–1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
b Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1 Kowakae, Higashi-osaka,
Osaka 577-8502, Japan
Received (in Cambridge, UK) 21st September 2000, Accepted 7th December 2000
First published as an Advance Article on the web 16th January 2001
The treatment of alkynylselenonium salt with benzenesulfinic acid in iPrOH gives (Z)-β-sulfonylvinylselenonium
salts in good yields. The alkenylselenonium salts thus prepared react with nucleophiles such as alkoxides, halides,
and acetylides to produce β-functionalized (Z)-vinyl sulfones in high yields. Furthermore, we succeeded in the
simple stereoselective one-step synthesis of various chiral (Z)-β-alkoxyvinyl sulfones by the use of chiral alcohols.
Table 1 The reactions of alkynylselenonium salts 1 with sodium
benzenesulfinate in protic solvents (see Scheme 1)
Introduction
Vinyl sulfones are one of the most important synthons in
organic synthesis because of their versatile utility,1 and
various synthetic methods towards vinyl sulfones have been
developed.1a–c,2 However, there have been few reports on the
introduction of a substituent at the β-position by manipulation
of a simple vinyl sulfone.3 In particular, Back et al. demon-
strated that the β-(phenylseleno)vinyl sulfones, prepared
by addition of Se-phenyl toluene-p-selenosulfonate to alkynes,
could be transformed into a variety of β-substituted vinyl
sulfones.4 Replacement of the SePh group was accom-
plished using selenocuprates RCu(SePh)Li or a combination
of m-chloroperbenzoic acid and nucleophiles to afford
β-functionalized vinyl sulfones with retention of configuration.
However, these methods have significant drawbacks. In the
former case, the selenocuprates have to be prepared by compli-
cated procedures, and, in the latter case, the range of usable
nucleophiles is limited. We attempted to prepare β-function-
alized vinyl sulfones using β-sulfonylvinylselenonium salts
because the selenonium group is an effective leaving group.
Since the synthesis and reactivity of vinylselenonium salts have
hardly been studied until now, we had great interest in them.5
Ochiai’s group had succeeded in the preparation of vinyl
sulfones based on a similar concept, namely that iodonium
group or the iodinane moieties are ‘hyperleaving groups.’6
We previously reported the reactions of diphenyl(phenyl-
ethynyl)selenonium triflate with several nucleophiles such as
carbanions,7 halides,8 and thiolate anions.9 In each case, the
selenonium moiety acted as a good leaving group and the
corresponding selenide was released. In this paper, we describe
the synthesis of β-sulfonylvinylselenonium salts and their
utilization for the preparation of various β-functionalized vinyl
sulfones.
Selenonium
salt
Temp.
(T/ЊC)
Products
(% yield)
Entry
Solvent
1
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1a
1b
1b
1b
1b
1b
EtOH
EtOH
EtOH
MeOH
iPrOH
EtOH
EtOH
EtOH
MeOH
iPrOH
rt
Ϫ78
60
rt
rt
2 (21) 4a (74)
2 (4) 4a (92)
2 (33) 4a (25) 5 (20)
2 (25) 4b (60)
2 (12) 4c (68)
3 (73) 4a (69) 5 (7)
3 (67) 4a (64)
3 (73) 4a (64) 5 (5)
3 (80) 4b (64) 5 (7)
3 (80) 4c (71) 5 (12)
rt
Ϫ78
60
rt
10
rt
tions of dimethyl- and diphenyl-alkynylselenonium salts with
sodium benzenesulfinate in various solvents were investigated
with the aim of a one-pot preparation of β-alkoxyvinyl sulfones
(Scheme 1). First, we conducted the reactions in alcohols as
Scheme 1
protic solvents. The results are shown in Table 1. The reactions
of dimethylalkynylselenonium salt 1a5d at room temperature
afforded (Z)-ethoxyvinyl sulfone 4a as the main product
together with methyl phenylethynyl selenide 2 as a minor
product produced by demethylation of 1a. The demethylation
product 2 was hardly obtained at all from the reaction at low
temperature in entry 2, and the yield of the desired compound
was very high, whereas the reaction at 60 ЊC gave 2 (33%), 4a
(25%), and 5 (20%). The reactions in other solvents at room
temperature also afforded (Z)-alkoxyvinyl sulfones 4b and 4c in
Results and discussion
It is known that alkenylselenonium salts act as useful Michael
acceptors toward nucleophiles.5b Alkynylselenonium salts are
expected to function similarly. On the other hand, sulfinic acids
and their sodium salts are good nucleophiles that easily under-
go nucleophilic attack on activated double bonds as well as
carbonyl compounds and alkyl halides.10 Therefore, the reac-
DOI: 10.1039/b007715l
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247
This journal is © The Royal Society of Chemistry 2001
239

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Table 2 The reactions of alkynylselenonium salts 1 and various alcohols with sodium benzenesulfinate in aprotic solvents (see Scheme 2)
Entry
1
R2OH (equiv.)
Solvent
Temp. (T/ЊC)
Time (t/h)
Products (% yield)a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
1a
1a
1a
1a
1b
p-NO2C6H4CH2OH (1.5)
p-NO2C6H4CH2OH (1.5)
p-NO2C6H4CH2OH (1.0)
THF
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
Ϫ30
rt
rt
3.0
3.0
0.5
0.5
0.33
0.5
0.33
1.0
2.0
2.0
0.5
18
Complex mixture
Complex mixture
4d (91) 3 (93)
4e (90) 3 (95)
4f (96) 3 (94)
4g (83) 3 (90)
4h (73) 3 (79)
4i (51) 3 (88) 5 (21) 6 (5)
4i (50) 3 (100) 5 (24) 6 (5)
4i (48) 3 (96) 5 (23) 6 (3)
4i (56) 2 (28) 5 (12) 6 (5)
4i (63) 2 (20) 5 (6)
4i (30) 2 (41) 5 (24) 6 (4)
4i (41) 2 (26) 5 (14) 6 (3)
3 (62) 5 (27) 6 (17)
DMSO
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
THF
PhCH2OH (1.5)
᎐
HC᎐CCH2OH (1.5)
᎐
(BrCH2)2CHOH (1.5)
Ph2CHOH (1.5)
( )-PhCH(Me)OH (1.5)
( )-PhCH(Me)OH (3.0)
( )-PhCH(Me)OH (5.0)
( )-PhCH(Me)OH (1.5)
( )-PhCH(Me)OH (1.5)
( )-PhCH(Me)OH (1.5)
( )-PhCH(Me)OH (1.5)
(Ϫ)-Menthol (1.0)
0.5
0.5
1.0
DMF
MeCN
rt
a Isolated yield based on selenonium salt 1.
good yields together with demethylation product 2. Next, we
conducted the reaction of diphenylalkynylselenonium salt 1b7a
with sodium benzenesulfinate under the same conditions as
mentioned above because selenonium salt 1a suffered some
demethylation. As we had expected, the dephenylation of 1b
did not occur, and the desired alkoxyvinyl sulfones were
obtained in good yields (entries 6–10). In some cases, a small
amount of (Z)-bis(phenylsulfonyl)styrene 5 was obtained as a
by-product. The geometrical structure of 4a was determined by
a nuclear Overhauser effect (NOE) experiment, which showed
enhancement of the ortho-protons of the Z-phenyl group
(11.4%) and of the methylene protons of the geminal ethoxy
group (7.5%) on irradiation of the vinyl proton.
yield of compound 4i (entries 9 and 10), the utilization of
dimethylalkynylselenonium salt 1a, which was less bulky than
1b, gave a somewhat better yield; MeCN was the best solvent
(entries 11–14). When the yield of β-alkoxyvinyl sulfone was
low, 1,2-bis(phenylsulfonyl)styrene 5 and divinyl ether deriv-
ative 6 were produced as by-products. The separation of the
desired compound and the by-products by TLC on silica gel
was very difficult. The β-alkoxyvinyl sulfones 4 shown in
Scheme 2 were only single geometrical isomers. The stereo-
chemistry of compound 4g was determined to be (Z) by the
NOE enhancement between the vinyl proton and the ortho-
protons of the Z-phenyl group (7.3%) or of the methyne
proton of the geminal 2-bromo-1-(bromomethyl)ethoxy group
(18.6%).
When an alcohol was used as solvent, the β-alkoxy group of
the product was derived from the solvent. In order to prepare
a variety of β-alkoxyvinyl sulfones, we examined the reactions
of alkynylselenonium salts 1 with various alcohols and sodium
benzenesulfinate in aprotic solvents (Scheme 2). The results are
Two kinds of reaction pathways for the formation of
β-alkoxyvinyl sulfones can be considered (Scheme 3). First,
Scheme 3
the Michael-type anti-addition of a sulfinate ion to alkynyl-
selenonium salts would form a (Z)-vinylselenonium ylide
intermediate. Route A contains the processes whereby proton-
ation of the ylide with an alcohol produces a (Z)-vinyl-
selenonium salt and its successive reaction with the resulting
alkoxide gives product 4. The latter process leading to (Z)-β-
alkoxyvinyl sulfones will be discussed in detail in Scheme 8. If
the reactions proceed through an alkylidene carbene intermedi-
ate in route B, phenyl phenylethynyl sulfone as a 1,2-rearrange-
ment product2d,11 and a mixture of (E)- and (Z)-β-alkoxyvinyl
sulfones as RO-H insertion products would be formed.12 How-
ever, alkynyl sulfone derivative and (E)-β-alkoxyvinyl sulfones
were not obtained from the reactions mentioned above, and
route B was thus excluded.
Scheme 2
summarized in Table 2. The reaction of 1b with p-nitrobenzyl
alcohol in MeCN at room temperature only for 30 minutes pro-
duced the desired (Z)-β-alkoxyvinyl sulfone 4d in a high yield
(entry 3), while a complex mixture was obtained when THF or
DMSO was used as solvent (entries 1 and 2). The reactions with
other primary alcohols also proceeded smoothly in a short reac-
tion time, and corresponding β-alkoxyvinyl sulfones 4e and 4f
were given efficiently (entries 4 and 5). However, the employ-
ment of bulkier secondary alcohols brought about a decreasing
yield of β-alkoxyvinyl sulfones 4g–i (entries 6–8), and, in
particular, no desired product was obtained when (Ϫ)-menthol,
a cyclic secondary alcohol, was used (entry 15). Although
increasing the amount of an alcohol could not improve the
Next, in order to elucidate the reaction mechanism via a
vinylselenonium salt intermediate, we tried to prepare vinyl-
selenonium salts and examine their reactivity. The reactions of
alkynylselenonium salts 1 with benzenesulfinic acid in propan-
2-ol gave (Z)-β-sulfonylalkenylselenonium salts 7 in good yields
240
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247

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Table 3 The reactions of alkenylselenonium salts 7 with alkoxides in
protic solvents (see Scheme 5)
Selenonium
salt
Alkoxide
(equiv.)
Products
(% yield)
Entry
Solvent
1
2
3
4
5
6
7a
7a
7a
7b
7b
7b
MeONa (1.0)
EtONa (1.0)
iPrONa (1.0)
MeONa (1.0)
EtONa (1.0)
iPrONa (1.0)
MeOH
EtOH
iPrOH
MeOH
EtOH
iPrOH
4b (82)
4a (80)
4c (70)
3 (75) 4b (71)
3 (79) 4a (75)
3 (92) 4c (89)
are valuable reagents in various asymmetric reactions15 and
syntheses.16 However, because chiral alcohols are expensive,
reactions with chiral alkoxides in aprotic solvents were
carried out (Scheme 6). These results are summarized in Table
Fig. 1 ORTEP drawing of 7b.
Scheme 4
(Scheme 4). The stereochemistry of 7 was determined as (Z) by
NOE measurement of 7b (8.0%) between the vinylic proton and
ortho-protons of the Z-phenyl group. These results indicated
that the alkynylselenonium salts underwent the anti-Michael-
type addition of benzenesulfinic acid in a similar way to the
general nucleophilic addition to alkynes.2d,13 The77Se NMR
spectrum showed a signal at δ 502.8 in CDCl3 due to the
selenonio group, which was shifted to lower field than that of
the alkynylselenonium salt 1b at δ 469.6 because of the more
electron-deficient double bond bearing a sulfonyl group.
Furthermore, the structure of salts 7 was established more
clearly by X-ray analysis of compound 7b (Fig. 1). The
Se(1) ؒ ؒ ؒ O (1) distance 3.074 Å is significantly shorter than the
sum of the van der Waals radii (3.40 Å) of selenium and oxygen
atoms. The O(5) ؒ ؒ ؒ Se(1)–C(1) angle of 163.9Њ is approximately
collinear, and the C(15)–Se(1)–C (21) bond angle is 99.7Њ. These
data suggested that a weak bonding interaction, such as hyper-
valent bonding, existed between the oxygen atom of the triflate
moiety and the selenium atom.5c,7a,14 Thus, the configuration of
the selenium atom was a slightly distorted trigonal bipyramid
in which the two phenyl groups and a lone pair occu-
pied equatorial positions and the structure was similar to a
selenurane rather than to a selenonium salt.
Scheme 6
4. The reaction of diphenylalkenylselenonium salt 7b with
(ϩ)-1-phenylethanol as an acyclic secondary alcohol in the
presence of NaH at Ϫ30 ЊC for 30 minutes afforded (Z)-β-
alkoxyvinyl sulfone 4i in 91% yield (entry 1). The reaction with
(ϩ)-3-chloro-1-phenylpropan-1-ol produced the desired com-
pound 4j in a very high yield (entry 4). The reactions of
alkenylselenonium salt 7b with achiral secondary alcohols gave
better results than those of alkynyl congener 1b (compare
entries 5 and 6 in Table 4 with entries 6 and 7 in Table 2).
Although dimethylalkenylselenonium salt 7a reacted with
(ϩ)-1-phenylethanol to afford 4i in a good yield, the results
were not satisfactory. These results showed that the use of
alkenylselenonium salts, compared with alkynylselenonium
salts, improved the yields of (Z)-β-alkoxyvinyl sulfones in the
reactions with bulky secondary alcohols. According to this pro-
cedure, we prepared chiral (Z)-β-cycloalkoxyvinyl sulfones,
which had not been obtained from the reactions of alkynyl-
selenonium salt 1b. The results are summarized in Table 5. The
reactions of diphenylvinylselenonium salt 7b with menthol and
NaH in MeCN did not give good results, and the yield of the
desired product 4k was up to 47% by use of 2 mole equivalents
of menthol (entries 1 and 2). On the other hand, dimethyl-
vinylselenonium salt 7a reacted with 1.2 mole equivalents of
menthol in the presence of NaH to produce 4k in only a 29%
yield because the remaining NaH, which did not completely
react with menthol, would decompose 7a (entry 3). Therefore,
the employment of excess of selenonium salt 7a improved the
yield of 4k, up to 67% (entries 4 and 5). Phenyllithium was used
as a base, and lithium menthoxide was effectively prepared. The
best result was obtained from the reaction of 1.5 mole equiv-
alents of 7a and menthol with phenyllithium in THF at Ϫ78 ЊC
(entry 7). Similarly, the reactions with bulky secondary cyclic
alcohols, (Ϫ)-borneol and (Ϫ)-trans 2-phenylcyclohexanol,
gave chiral (Z)-β-cycloalkoxyvinylsulfones 4l and 4m in
excellent yields (entries 8 and 9).
We examined the reactions of the (Z)-β-sulfonylalkenyl-
selenonium salts 7 thus prepared with alkoxides in alcohols as
a protic solvent (Scheme 5). Either dimethyl- or diphenyl-
Scheme 5
selenonium salt 7a, 7b reacted smoothly with alkoxides pre-
pared from NaH and the corresponding alcohols to produce
(Z)-β-alkoxyvinyl sulfones 4 in high yields with retention of
configuration. Demethylation of dimethylalkenylselenonium
salt 7a was not observed in the reactions (Table 3). Next, we
planned to apply this synthetic method to prepare chiral (Z)-O-
alkyl enol ethers bearing the phenylsulfonyl group at the
β-position by using chiral alcohols. Chiral O-alkyl enol ethers
Next, we investigated the reactions of vinylselenonium
salts with other nucleophiles (Scheme 7). First, reactions with
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247
241

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Table 4 The reactions of alkenylselenonium salts 7 with alkoxides in MeCNa (see Scheme 6)
Selenonium
salt
Temp
(T/ЊC)
Time
(t/h)
Product
Entry
R2OH
(% yield)b
Optical rotation
1
2
3
4
5
6
7b
7a
7a
7b
7b
7b
(ϩ)-PhCH(Me)OH
(ϩ)-PhCH(Me)OH
(ϩ)-PhCH(Me)OH
(ϩ)-ClCH2CH2CHPhOH
(BrCH2)2CHOH
Ϫ30
0.5
0.5
0.5
2
0.5
0.5
4i (91)
4i (62)
4i (65)
4j (88)
4g (91)
4h (90)
[α]D26 Ϫ94.9 (c 1.19 in CHCl3)
0
Ϫ30
Ϫ30
Ϫ30
Ϫ30
[α]D28 Ϫ40.8 (c 2.18 in CHCl3)
—
—
Ph2CHOH
a Conditions: 1 equiv. of selenonium salt 7, 1.1 equiv. of an alcohol and NaH in MeCN. b Isolated yield based on selenonium salt 7.
Table 5 The reactions of alkenylselenonium salts 7 with cyclic secondary alcoholsa (see Scheme 6)
Selenonium
salt (equiv.)
Temp.
(T/ЊC)
Product
(% yield)
Entry
ROH (equiv.)
Base
Solvent
Optical rotation
1
2
3
4
5
6
7
8
9
7b (1)
(Ϫ)-Menthol (1.5)
(Ϫ)-Menthol (2.0)
(Ϫ)-Menthol (1.2)
(Ϫ)-Menthol (1)
(Ϫ)-Menthol (1)
(Ϫ)-Menthol (1)
(Ϫ)-Menthol (1)
(Ϫ)-Borneol (1)
(Ϫ)-trans-2-Phenylcyclohexanol
NaH
NaH
NaH
NaH
NaH
PhLi
PhLi
PhLi
PhLi
MeCN
MeCN
MeCN
MeCN
MeCN
THF
THF
THF
THF
Ϫ30
Ϫ30
Ϫ30
Ϫ30
Ϫ30
Ϫ78
Ϫ78
Ϫ78
Ϫ78
4k (39)b
4k (47)b
4k (29)b
4k (58)c
4k (67)c
4k (64)c
4k (80)c
4l (96)c
4m (90)c
[α]D26 Ϫ28.6 (c 1.44 in CHCl3)
7b (1)
7a (1)
7a (1.5)
7a (3.0)
7a (1.0)
7a (1.5)
7a (1.5)
7a (1.5)
[α]D29 Ϫ37.6 (c 1.61 in CHCl3)
[α]D30 Ϫ179.7 (c 0.55 in CHCl3)
a These reactions were carried out for 12 h. b Isolated yield based on selenonium salt 7. c Isolated yield based on alcohols.
Table 6 The reactions of alkenylselenonium salts 7 with halides (see Scheme 7)
Selenonium
salt
Nucleophile
(equiv.)
Products
(% yield)
Entry
Solvent
1
2
3
4
5
6
7
8
9
7a
7a
7b
7b
7b
7b
7b
7b
7b
7b
nBu4NBr (1)
LiBr (1)
CHCl3
MeCN
CHCl3
CHCl3
CHCl3
MeCN
MeCN
MeCN–MeOH
MeCN–MeOH
MeCN–MeOH
8 (90)
8 (88)
nBu4NI (1)
nBu4NBr (1)
nBu4NCl (1)
NaI (2)
3 (94) 4n (91)
3 (90) 4o (92)
3 (85) 4p (88)
3 (75) 4n (76)
3 (86) 4o (85)
3 (71) 4o (62)
3 (43) 4o (39)
3 (53) 4p (45)
LiBr (1)
NaBr (2)
KBr (2)
10
NaCl (2)
Table 7 The reactions of diphenylalkenylselenonium salt 7b with
acetylides (see Scheme 7)
Nucleophile
(equiv.)
Temp.
(T/ЊC)
Products
(% yield)
Entry
Solvent
᎐
1
2
3
PhC᎐CLi (1.2)
THF
THF
THF
Ϫ78
Ϫ78
Ϫ78
3 (73)
3 (86)
3 (82)
4p (52)
4r (49)
4s (53)
᎐
n
᎐
BuC᎐CLi (1.2)
᎐
t
᎐
BuC᎐CLi (1.2)
᎐
NOE measurement of 4n, which showed enhancement (5.3%)
between the vinylic proton and ortho-protons of the Z-phenyl
group. The reactivity of acetylides as carbanions with the
vinylselenonium salts was also examined (Table 7). The reaction
of diphenylvinylselenonium salt 7b with 1.2 mole equivalents of
lithium phenylacetylide, prepared from the reaction of phenyl-
acetylene and n-butyllithium in THF at Ϫ78 ЊC, afforded
(Z)-β-alkynylvinyl sulfone 4q in 52% yield (entry 1). The reac-
tions with other acetylides similarly gave corresponding
(Z)-enyne sulfone derivatives in good yields (entries 2 and 3).
The Z configuration was determined by NOE experiment on 4s,
showing the enhancement of the ortho-protons of the Z-phenyl
group (6.1%) upon irradiation of the vinyl proton.
Scheme 7
various halides were conducted (Table 6). The reaction of
dimethylvinylselenonium salt 7a with tetrabutylammonium
bromide as a phase-transfer catalyst or lithium bromide as an
inorganic salt gave the demethylation product 8 in high yields,
while the β-halogenovinyl sulfone was not obtained at all
(entries 1 and 2). In contrast, the reactions of diphenylvinyl-
selenonium salt 7b proceeded easily to produce corresponding
(Z)-β-halogenovinyl sulfones 4n–p in high yields except with
sodium chloride or potassium bromide because of their insolu-
bility in organic solvents (entries 3–10). The stereochemistry of
the β-halogenovinyl sulfones was determined as being Z by
A plausible mechanism for the formation of the β-substi-
tuted (Z)-vinyl sulfones 4 from the reactions of vinylselenon-
ium salts 7 with nucleophiles is shown in Scheme 8. Route A
proceeds via the pathway whereby the Michael-type addition of
242
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Dimethyl(phenylethynyl)selenonium tetrafluoroborate 1a
Trimethyloxonium tetrafluoroborate (2.04 g, 13.8 mmol) was
added to a stirred solution of methyl phenylethynyl selenide19
(2.54 g, 13.8 mmol) in dichloromethane (10 cm3) at room
temperature. The mixture was stirred in an atmosphere of
nitrogen overnight. After the solvent had been evaporated
under reduced pressure, the residue was washed with diethyl
ether several times and purified by recrystallization from
dichloromethane–diethyl ether to give the selenonium salt 1a
(2.54 g, 62%) as colourless prisms, mp 132–135 ЊC (Found: C,
40.4; H, 3.7. C10H11BF4Se requires C, 40.5; H, 3.7%); νmax
(KBr)/cmϪ1 2180 and 1140–1040; δH (400 MHz; CDCl3) 3.33
(6 H, s, SeCH3), 7.41 (2 H, t, J 7.3, ArH), 7.51 (1 H, t, J 7.3,
ArH) and 7.59 (2 H, d, J 7.3, ArH); δC (100 MHz; CD3CN) 29.0
(q), 65.3 (s), 104.8 (s), 119.6 (s), 129.9 (d), 132.8 (d) and 133.5
(d); m/z (FAB) 221 ([M Ϫ BF4]ϩ, 100%) and 136 (53).
Scheme 8
General procedure for the reactions of alkynylselenonium salts
with sodium benzenesulfinate in alcohols. A typical example
(Table 1, entry 1): (Z)-ꢀ-ethoxy-ꢁ-(phenylsulfonyl)styrene 4a
a nucleophile to the β-carbon in the vinyl sulfonyl moiety forms
betaine 9 and the subsequent elimination of a selenide leads to
the (Z)-vinyl sulfones with retention of configuration.6b,17
Another pathway, route B, involves the formation of the selen-
urane intermediate 10, via direct attack of the nucleophile to
the selenium atom in the vinylselenonium salt, followed by
ligand coupling between the Nu and the vinyl group of 10.18
Both pathways provide feasible explanations of the stereo-
chemical outcome observed in these reactions. On the other
hand, demethylation product 8 was formed by the SN2 reaction
shown because the selenonio group was a good leaving group.
Sodium benzenesulfinate (82 mg, 0.5 mmol) was added to a
stirred solution of the dimethyl(phenylethynyl)selenonium
tetrafluoroborate 1a (148 mg, 0.5 mmol) in ethanol (5 cm3) at
room temperature. The resulting mixture was stirred at the
same temperature for 3 h, poured into water and extracted with
ethyl acetate. The extracts were washed with brine and dried
over MgSO4. After the solvent had been evaporated under
reduced pressure, the residue was separated by PLC (5:1
hexane–ethyl acetate) to give 2 (20 mg, 21%) and the vinyl sul-
fone 4a (107 mg, 74%). Compound 4a: colourless oil [HRMS
Calc. for C16H16O3S: M, 288.0820. Found: Mϩ, 288.0809]; νmax
(NaCl)/cmϪ1 1631, 1302, 1227, 1150 and 1084; δH (400 MHz;
CDCl3) 1.23 (3 H, t, J 6.8, CH2CH3), 3.99 (2 H, q, J 6.8,
Conclusions
We showed that (Z)-β-sulfonylvinylselenonium salts, which
were prepared easily from the reaction of alkynylselenonium
salts with benzenesulfinic acid in iPrOH, acted as useful
intermediates in the synthesis of β-functionalized (Z)-vinyl
sulfones. By means of this method, we developed a simple,
efficient, and stereoselective one-step synthesis of various
(Z)-β-substituted vinyl sulfones in good yields. In particular, it
is very valuable that the Z configuration products, which are
thermodynamically unstable, are accessible, and that diphenyl
selenide, which was recovered in a high yield, was reused as
one of the starting materials for the preparation of alkynyl-
selenonium salt 1b.
CH CH ), 6.57 (1 H, s, C᎐CH), 7.30–7.40 (5 H, m, ArH), 7.46
᎐
2
3
(2 H, t, J 7.3, ArH), 7.56 (1 H, t, J 7.3, ArH) and 7.90 (2 H, d,
J 7.3, ArH); δC (68 MHz; CDCl3) 14.8 (q), 71.3 (t), 121.2 (s),
127.4 (d), 127.9 (d), 128.0 (d), 128.2 (d), 130.6 (d), 131.5 (s),
132.5 (d), 142.2 (s) and 154.7 (d); m/z (EI) 288 (Mϩ, 100%),
260 (40), 119 (65) and 91 (83).
(Z)-ꢀ-Methoxy-ꢁ-(phenylsulfonyl)styrene 4b. White powder,
mp 89–90 ЊC (Found: C, 65.6; H, 5.3. C15H14O3S requires C,
65.7; H, 5.1%); νmax (NaCl)/cmϪ1 1625, 1305, 1250, 1132 and
1081; δH (400 MHz; CDCl3) 3.82 (3 H, s, CH3), 6.51 (1 H, s,
C᎐CH), 7.27–7.35 (5 H, m, ArH), 7.47 (2 H, t, J 7.3, ArH), 7.56
᎐
(1 H, t, J 7.3, ArH) and 7.87 (2 H, d, J 7.3, ArH); δC (100 MHz;
CDCl3) 62.5 (q), 121.8 (s), 127.6 (d), 128.2 (d), 128.4 (d), 128.5
(d), 131.0 (d), 131.7 (s), 132.7 (d), 142.5 (s) and 155.9 (d); m/z
(EI) 274 (Mϩ, 75%) and 118 (100).
Experimental
General
Mps were obtained with a Yanagimoto micro melting point
apparatus and are uncorrected. IR spectra of solids (KBr) and
liquids (NaCl) were recorded on a JASCO IRA-100 spectro-
(Z)-ꢀ-Isopropoxy-ꢁ-(phenylsulfonyl)styrene 4c. White powder,
mp 91–94 ЊC (Found: C, 67.4; H, 6.0. C17H18O3S requires C,
67.5; H, 6.0%); νmax (NaCl)/cmϪ1 1623, 1305, 1227, 1145 and
1082; δH (400 MHz; CDCl3) 1.19 (6 H, d, J 6.4, CH3CHCH3),
1
photometer. H NMR spectra were recorded on a JEOL GX-
270 (270 MHz) or a JEOL EX-400 (400 MHz) spectrometer
with tetramethylsilane as internal standard. 13C NMR spectra
were recorded on the JEOL GX-270 (68 MHz) or the JEOL
EX-400 (100 MHz) spectrometer with chloroform as internal
standard. The 77Se NMR spectrum of salt 7b was recorded
on the JEOL EX-400 (76 MHz) spectrometer with dimethyl
selenide as external standard. The J-values are given in Hz.
Mass spectra (MS and HRMS) were obtained with electron
impact (EI, 70 eV) or fast-atom bombardment (FAB, glycerol or
3-nitrobenzyl alcohol as matrix) techniques. Elemental analyses
of new compounds were performed by a Yanaco CHN Corder
MT-5. Optical rotations were measured on a JASCO DIP-360
digital polarimeter for CHCl3 solution. All chromatographic
isolations were accomplished with either Kieselgel 60 (Merck)
or BW-127ZH (Fuji Silysia) for column chromatography or
Kieselgel 60 PF254 containing gypsum (Merck) for preparative
TLC (PLC).
4.09 (1 H, m, J 6.4, CH CHCH ), 6.60 (1 H, s, C᎐CH),
᎐
3
3
7.32–7.40 (5 H, m, ArH), 7.47 (2 H, t, J 7.3, ArH), 7.56 (1 H, t,
J 7.3, ArH) and 7.93 (2 H, d, J 7.3, ArH); δC (68 MHz; CDCl3)
22.0 (q), 78.6 (t), 121.5 (s), 127.7 (d), 128.01 (d), 128.04 (d),
128.1 (d) 130.6 (d), 131.7 (s), 132.5 (d), 142.7 (s) and 153.4 (d);
m/z (EI) 302 (Mϩ, 20%), 260 (100) and 119 (47).
(Z)-ꢁ,ꢀ-Bis(phenylsulfonyl)styrene 5. Colourless needles, mp
83–85 ЊC {HRMS Calc. for C20H17O4S2: ([M ϩ H]ϩ), 385.0568.
Found: m/z, 385.0564}; νmax (NaCl)/cmϪ1 1583, 1331 and 1159;
δH (400 MHz; CDCl ) 6.88 (1 H, s, C᎐CH), 7.20 (2 H, d,
᎐
3
J 7.3, ArH), 7.26 (2 H, t, J 7.8, ArH), 7.35–7.48 (3 H, m,
ArH), 7.55–7.61 (3 H, m, ArH), 7.67–7.73 (3 H, m, ArH)
and 8.10 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 128.2 (q),
128.3 (d), 128.9 (d), 129.1 (d), 129.2 (d), 129.5 (d), 130.3 (d),
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247
243

View Article Online
132.4 (s), 133.9 (d), 134.3 (d), 138.1 (s), 140.8 (d), 141.4 (s) and
152.2 (s); m/z (FAB) 385 ([M ϩ H]ϩ, 55%), 289 (19) and 136
(60).
122.9 (s), 127.0 (d), 127.9 (d), 128.2 (d), 128.4 (d), 128.5 (d),
128.7 (s), 130.9 (d), 131.7 (s), 132.6 (d), 139.4 (s), 142.6 (s) and
153.1 (d); m/z (FAB) 427 ([M ϩ H]ϩ, 3%), 167 (100) and 136
(35).
General procedure for the reactions of alkynylselenonium salts
and various alcohols with sodium benzenesulfinate in aprotic
solvents. A typical example (Table 2, entry 3): (Z)-ꢀ-(p-nitro-
benzyloxy)-ꢁ-(phenylsulfonyl)styrene 4d
{(Z)-ꢀ-(1-Phenylethoxy)-ꢁ-(phenylsulfonyl)styrene 4i. White
powder, mp 92–93 ЊC (Found: C, 72.3; H, 5.6. C22H20O3S
requires C, 72.5; H, 5.5%); νmax (NaCl)/cmϪ1 1632, 1304 and
1145; δH (400 MHz; CDCl3) 1.59 (3 H, d, J 6.8, CH3), 4.95 (1 H,
Sodium benzenesulfinate (36 mg, 0.22 mmol) was added to a
stirred solution of diphenyl(phenylethynyl)selenonium trifluoro-
methanesulfonate 1b (97 mg, 0.2 mmol) and p-nitrobenzyl
alcohol (31 mg, 0.2 mmol) in acetonitrile (3 cm3) at room
temperature. The resulting mixture was stirred at the same tem-
perature for 0.5 h, poured into water and extracted with ethyl
acetate. The extracts were washed with brine and dried over
MgSO4. After the solvent had been evaporated under reduced
pressure, the residue was separated by PLC (chloroform) to give
3 (43 mg, 93%) and the vinyl sulfone 4d (72 mg, 91%). 4d:
colourless prisms, mp 113–114 ЊC (Found: C, 63.7; H, 4.5; N,
3.5. C21H17NO5S requires C, 63.8; H, 4.3; N, 3.5%); νmax (NaCl)/
cmϪ1 1620, 1520, 1350, 1280 and 1139; δH (400 MHz; CDCl3)
q, J 6.8, OCH), 6.53 (1 H, s, C᎐CH), 7.05–7.07 (2 H, m, ArH),
᎐
7.25–7.30 (8 H, m, ArH), 7.49 (2 H, t, J 7.3, ArH), 7.60 (1 H, t,
J 7.3, ArH) and 7.96 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3)
23.3 (q), 83.6 (d), 122.4 (s), 125.8 (d), 128.1 (d), 128.2 (d), 128.3
(d), 128.4 (d), 128.5 (d), 128.7 (d), 130.8 (d), 131.8 (s), 132.7 (d),
140.9 (s), 142.8 (s) and 153.2 (d); m/z (FAB) 365 ([M ϩ H]ϩ,
12%), 261 (25) and 136 (62).
Bis[(Z)-2-phenyl-2-(phenylsulfonyl)vinyl ether 6. White
powder, mp 152–155 ЊC (Found: C, 67.0; H, 4.5. C28H22O5S2
requires C, 66.9; H, 4.4%); νmax (NaCl)/cmϪ1 1607, 1318 and
1170; δH (400 MHz; CDCl3) 6.66 (2 H, s, C᎐CH), 7.24 (4 H, d,
᎐
J 7.3, ArH), 7.32 (4 H, t, J 7.3, ArH), 7.38 (2 H, d, J 7.3, ArH),
7.55 (4 H, t, J 7.3, ArH), 7.63 (2 H, t, J 7.3, ArH) and 8.17 (4 H,
d, J 7.3, ArH); δC (100 MHz; CDCl3) 127.1 (s), 128.3 (d), 128.4
(d), 129.1 (d), 129.3 (d), 130.6 (s), 131.0 (d), 133.5 (d), 140.9 (s)
and 149.4 (d); m/z (FAB) 503 ([M ϩ H]ϩ, 40%), 289 (15) and
136 (65).
5.12 (2 H, s, OCH ), 6.63 (1 H, s, C᎐CH), 7.27–7.39 (7 H, m,
᎐
2
ArH), 7.43 (2 H, t, J 7.8, ArH), 7.57 (1 H, t, J 7.3, ArH), 7.84
(2 H, d, J 7.3, ArH) and 8.16 (2 H, d, J 8.8, ArH); δC (100 MHz;
CDCl3) 75.1 (t), 123.4 (s), 123.8 (d), 127.5 (d), 127.6 (d), 128.2
(d), 128.6 (d), 128.7 (d), 130.8 (d), 131.1 (s), 132.9 (d), 142.1 (s),
142.5 (s), 147.7 (s) and 153.5 (d); m/z (EI) 395 (Mϩ, 17%), 254
(54), 125 (78) and 77 (100).
General procedure for the synthesis of alkenylselenonium salts. A
typical example: (Z)-diphenyl[(Z)-2-phenyl-2-(phenylsulfonyl)-
vinyl]selenonium trifluoromethanesulfonate 7b
(Z)-ꢀ-Benzyloxy-ꢁ-(phenylsulfonyl)styrene 4e. White powder,
mp 107–108 ЊC (Found: C, 71.8; H, 5.2. C21H18O3S requires C,
72.0; H, 5.2%); νmax (NaCl)/cmϪ1 1635, 1301 and 1143; δH(400
Benzenesulfinic acid (1.05 g, 7.2 mmol) was added to a stirred
solution of diphenyl(phenylethynyl)selenonium trifluoro-
methanesulfonate 1b (2.90 g, 6.0 mmol) in propan-2-ol (70 cm3)
at room temperature. The mixture was stirred in an atmosphere
of argon for 12 h. After the solvent had been evaporated under
reduced pressure, the residue was washed with diethyl ether
several times and purified by recrystallization from dichloro-
methane–diethyl ether to give the selenonium salt 7b (2.99 g,
79%) as colourless prisms, mp 167 ЊC (Found: C, 51.8; H, 3.6.
C27H21F3O5S2Se requires C, 51.8; H, 3.4%); νmax (KBr)/cmϪ1
1340–1220 and 1150; δH (400 MHz; CDCl3) 7.22 (1 H, s,
MHz; CDCl ) 4.99 (2 H, s, OCH ), 6.63 (1 H, s, C᎐CH), 7.13–
᎐
3
2
7.15 (2 H, m, ArH), 7.26–7.35 (8 H, m, ArH), 7.39 (2 H, t, J 7.3,
ArH), 7.53 (1 H, t, J 7.3, ArH) and 7.84 (2 H, d, J 7.3, ArH);
δC 100 MHz; CDCl3) 76.7 (t), 122.5 (s), 127.4 (d), 127.7 (d),
128.2 (d), 128.4 (d), 128.5 (d), 128.6 (d), 128.7 (d), 130.8 (s),
131.6 (s), 132.7 (d), 135.2 (s), 142.5 (s) and 154.1 (d); m/z (FAB)
351 ([M ϩ H]ϩ, 14%), 289 (20) and 136 (55).
(Z)-ꢁ-Phenylsulfonyl-ꢀ-(prop-2-ynyloxy)styrene 4f. Pale yel-
low oil (Found: C, 68.3; H, 4.7. C17H14O3S requires C, 68.4; H,
4.7%); νmax (NaCl)/cmϪ1 2125, 1628, 1306 and 1142; δH (400
C᎐CH), 7.28 (2 H, t, J 7.3, ArH), 7.36 (1 H, t, J 7.3, ArH), 7.42
᎐
(2 H, t, J 7.3, ArH), 7.52–7.57 (3 H, m, ArH), 7.60–7.68 (6 H,
m, ArH), 7.76 (2 H, d, J 7.3, ArH) and 7.85 (4 H, d, J 7.3, ArH);
δC (100 MHz; CDCl3) 120.7 (q), 127.2 (d), 129.0 (d), 129.4 (d),
129.5 (d), 129.6 (d), 129.9 (s), 130.5 (d), 131.2 (d), 131.5 (d),
131.6 (s), 133.2 (d), 134.9 (s), 135.2 (d) and 155.0 (s); δSe (76
MHz; CDCl3) 502.8; m/z (FAB) 477 ([M Ϫ TfO]ϩ, 75%) and
136 (63).
᎐
MHz; CDCl ) 2.55 (1 H, t, J 2.4, C᎐CH), 4.58 (2 H, d, J 2.4,
᎐
3
OCH ), 6.72 (1 H, s, C᎐CH), 7.27–7.38 (5 H, m, ArH), 7.46
᎐
2
(2 H, t, J 7.3, ArH), 7.56 (1 H, t, J 7.3, ArH) and 7.87 (2 H, d,
J 7.3, ArH); δC (100 MHz; CDCl3) 61.3 (t), 76.5 (d), 77.6 (s),
123.9 (s), 127.7 (d), 128.3 (d), 128.5 (d), 128.6 (d), 130.9 (d),
131.5 (s), 132.9 (d), 142.2 (s) and 152.3 (d); m/z (FAB) 299
([M ϩ H]ϩ, 20%) and 136 (62).
Dimethyl[(Z)-2-phenyl-2-(phenylsulfonyl)vinyl]selenonium
tetrafluoroborate 7a. Colourless needles (from acetone–diethyl
ether), mp 174–176 ЊC (Found: C, 43.7; H, 3.9. C16H17BF4-
O2SSe requires C, 43.8; H, 3.9%); νmax (KBr)/cmϪ1 1350, 1150
and 1100–1050; δH (400 MHz; CDCl3) 3.19 (6 H, s, SeCH3),
(Z)-ꢀ-[2-Bromo-1-(bromomethyl)ethoxy]-ꢁ-(phenylsulfonyl)-
styrene 4g. Colourless plates, mp 103–105 ЊC (Found: C, 44.2;
H, 3.5. C17H16Br2O3S requires C, 44.4; H, 3.5%); νmax (KBr)/
cmϪ1 1634, 1287 and 1142; δH (400 MHz; CDCl3) 3.44 (2 H, dd,
J 6.4 and 11.2, CH2Br), 3.55 (2 H, dd, J 5.4 and 11.2, CH2Br),
7.08 (1 H, s, C᎐CH), 7.28 (2 H, t, J 7.3, ArH), 7.37 (1 H, t, J 7.3,
᎐
4.15–4.21 (1 H, m, OCH), 6.63 (1 H, s, C᎐CH), 7.30–7.40 (5 H,
᎐
ArH), 7.42–7.47 (4 H, m, ArH), 7.57 (1 H, t, J 7.3, ArH) and
7.73 (2 H, d, J 7.3, ArH); δC (100 MHz; CD3OD) 26.5 (q), 129.7
(d), 129.9 (d), 130.5 (d), 130.6 (d), 131.8 (d), 132.0 (s), 136.3 (d),
137.4 (s) and 154.1 (s); m/z (FAB) 353 ([M Ϫ BF4]ϩ, 100%) and
136 (73).
m, ArH), 7.48 (2 H, t, J 7.3, ArH), 7.59 (1 H, t, J 7.3, ArH) and
7.93 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 31.2 (t), 84.2
(d), 123.5 (s), 128.0 (d), 128.4 (d), 128.6 (d), 128.7 (d), 130.8 (d),
131.2 (s), 133.0 (d), 142.3 (s) and 152.3 (d); m/z (FAB) 461
([M ϩ 2 ϩ H]ϩ, 33%), 261 (40) and 136 (62).
General procedure for the reactions of alkenylselenonium salts
with alkoxides in protic solvents. A typical example (Table 3,
entry 1): (Z)-ꢀ-methoxy-ꢁ-(phenylsulfonyl)styrene 4b
(Z)-ꢀ-Diphenylmethoxy-ꢁ-(phenylsulfonyl)styrene 4h. Colour-
less prisms, mp 146–148 ЊC (Found: C, 76.0; H, 5.3. C27H22O3S
requires C, 76.0; H, 5.2%); νmax (NaCl)/cmϪ1 1625, 1306
and 1143; δH (400 MHz; CDCl3) 5.89 (1 H, s, OCH), 6.69 (1 H,
After 60% sodium hydride (8 mg, 0.2 mmol) had been added
to methanol (3 cm3) and the solution was strirred at room
temperature for 0.5 h, dimethyl(phenylethynyl)selenonium
s, C᎐CH), 7.24–7.36 (17 H, m, ArH), 7.51 (1 H, t, J 7.3, ArH)
᎐
and 7.85 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 88.5 (d),
244
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247

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tetrafluoroborate 7a (88 mg, 0.2 mmol) was added under argon.
The resulting mixture was stirred at the same temperature for
3 h, poured into water and extracted with ethyl acetate. The
extracts were washed with brine and dried over MgSO4. After
the solvent had been evaporated under reduced pressure, the
residue was separated by PLC (hexane–ethyl acetate 3:1) to
give the vinyl sulfone 4b (45 mg, 82%).
1622, 1318, 1250 and 1141; δH (400 MHz; CDCl3) 0.67 (3 H, d,
J 6.8, CH3), 0.84 (3 H, d, J 6.8, CH3), 0.88 (3 H, d, J 6.8, CH3),
0.80–1.00 (2 H, m, CH), 1.23–1.39 (3 H, m, CH), 1.64 (2 H, br
d, J 12.2, CH), 1.70–1.78 (1 H, m, CH), 1.85 (1 H, br d, J 12.2,
CH), 3.60 (1 H, dt, J 4.4 and 10.7, OCH), 6.64 (1 H, s, C᎐CH),
᎐
7.34–7.39 (5 H, m, ArH), 7.47 (2 H, t, J 7.3, ArH), 7.56 (1 H, t,
J 7.3, ArH) and 7.91 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3)
15.8 (q), 20.8 (q), 21.8 (q), 22.9 (t), 25.2 (d), 31.5 (d), 33.8 (d),
41.5 (t), 47.4 (d), 86.8 (d), 121.3 (s), 127.8 (d), 128.2 (d), 128.3
(d), 130.8 (d), 131.2 (s), 132.5 (d), 143.1 (s) and 154.1 (d);
m/z (FAB) 399 ([M ϩ H]ϩ, 10%), 261 (40) and 136 (58).
General procedure for the reactions of alkenylselenonium salts
with alkoxides in aprotic solvents. A typical example (Table 4,
entry 4): (Z)-ꢀ-[(1R)-3-chloro-1-phenylpropoxy]-ꢁ-(phenyl-
sulfonyl)styrene 4j
(Z)-ꢀ-[(1S,2R,4S)-Bornan-2-yloxy]-ꢁ-(phenylsulfonyl)styrene
4l. Colourless oil {HRMS Calc. for C24H29O3S ([M ϩ H]ϩ),
397.1837. Found: m/z 397.1833}; νmax (NaCl)/cmϪ1 1624, 1306
and 1143; δH (400 MHz; CDCl3) 0.80 (3 H, s, CH3), 0.83 (3 H, s,
CH3), 0.86 (3 H, s, CH3), 1.07 (1 H, dd, J 2.9 and 13.4, CH),
1.24–1.32 (2 H, m, CH), 1.67 (1 H, t, J 4.4, CH), 1.70–1.80 (1 H,
m, CH), 1.93–2.22 (1 H, m, CH), 2.14–2.23 (1 H, m, CH), 4.10
After 60% sodium hydride (5 mg, 0.11 mmol) had been added
to a stirred solution of (ϩ)-3-chloro-1-phenylpropan-1-ol (19
mg, 0.11 mmol) in acetonitrile (3 cm3) and the solution
stirred at room temperature for 1 h, diphenyl(phenylethynyl)-
selenonium trifluoromethanesulfonate 7b (63 mg, 0.1 mmol)
was added under argon. The resulting mixture was stirred at
the same temperature for 2 h, poured into water and extracted
with ethyl acetate. The extracts were washed with brine and
dried over MgSO4. After the solvent had been evaporated under
reduced pressure, the residue was separated by PLC (chloro-
form) to give the vinyl sulfone 4j (37 mg, 88%) as a pale yellow
oil {HRMS Calc. for C23H22ClO3S: [M ϩ Hϩ] 413.0978. Found:
m/z 413.0973}; νmax (NaCl)/cmϪ1 1626, 1305 and 1143; δH (400
MHz; CDCl3) 2.05–2.14 (1 H, m, CH2CH2Cl), 2.29–2.38 (1 H,
m, CH2CH2Cl), 3.42–3.49 (1 H, m, CH2CH2Cl), 3.55–3.62 (1 H,
m, CH2CH2Cl), 5.06 (1 H, dd, J 4.4 and 12.8, OCHPh), 6.55
(1 H, br d, J 4.4, OCH), 6.62 (1 H, s, C᎐CH), 7.32–7.38 (5 H, m,
᎐
ArH), 7.47 (2 H, t, J 7.3, ArH), 7.55 (1 H, t, J 7.3, ArH) and
7.91 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 13.1 (q), 18.5
(q), 19.4 (q), 26.4 (t), 27.7 (t), 35.7 (t), 44.4 (d), 47.9 (s), 49.6 (s),
92.8 (d), 120.1 (s), 127.2 (d), 127.9 (d), 128.3 (d), 130.6 (d), 131.9
(s), 132.4 (d), 142.9 (s) and 155.3 (d); m/z (FAB) 397 ([M ϩ H]ϩ,
8%), 289 (23) and 137 (65).
General procedure for the reactions of alkenylselenonium salt 7a
with halides. A typical example (Table 6, entry 2): (Z)-ꢀ-methyl-
seleno-ꢁ-(phenylsulfonyl)styrene 8
(1 H, s, C᎐CH), 7.07–7.11 (2 H, m, ArH), 7.22–7.33 (8 H, m,
᎐
ArH), 7.50 (2 H, t, J 7.3, ArH), 7.60 (1 H, t, J 7.3, ArH) and
7.93 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 40.1 (t), 40.6 (t),
84.1 (d), 122.6 (s), 126.0 (d), 127.7 (d), 128.2 (d), 128.4 (d) 128.6
(d), 128.7 (d), 128.9 (d), 130.8 (d), 131.4 (s), 132.8 (d), 138.7 (s),
142.8 (s) and 153.2 (d); m/z (FAB) 413 ([M ϩ H]ϩ, 25%), 261
(55) and 136 (67).
Lithium bromide (17 mg, 0.20 mmol) was added to a stirred
solution
of
dimethyl[2-phenyl-2-(phenylsulfonyl)vinyl]-
selenonium tetrafluoroborate 7a (88 mg, 0.20 mmol) in
acetonitrile (3 cm3) at room temperature. The resulting mixture
was stirred at the same temperature for 5 h, poured into water
and extracted with ethyl acetate. The extracts were washed with
brine and dried over MgSO4. After the solvent had been evap-
orated under reduced pressure, the residue was separated by
PLC (5:1 hexane–ethyl acetate) to give the vinyl sulfone 8 (59
mg, 88%) as yellow powder, mp 110–112 ЊC (Found: C, 53.2; H,
4.2. C15H14O2SSe requires C, 53.4; H, 4.2%); νmax (NaCl)/cmϪ1
1554, 1299 and 1143; δH (400 MHz; CDCl3) 2.22 (3 H, s,
SeCH3), 7.17–7.31 (5 H, m, ArH), 7.37 (2 H, t, J 7.3, ArH), 7.42
General procedure for the reactions of alkenylselenonium salt 7a
with cyclic secondary alkoxides. A typical example (Table 5,
entry 9): (Z)-ꢀ-[(1R,2S)-2-phenylcyclohexyloxy]-ꢁ-(phenyl-
sulfonyl)styrene 4m
After phenyllithium in cyclohexane–diethyl ether solution (0.85
mol dmϪ3) (0.47 cm3, 0.40 mmol) had been added to a stirred
solution of (Ϫ)-trans-2-phenylcyclohexanol (71 mg, 0.40 mmol)
in THF (1 cm3) and the solution strirred at Ϫ78 ЊC for 1 h, the
solution was added to a stirred solution of dimethyl(phenyl-
ethynyl)selenonium tetrafluoroborate 7a (179 mg, 0.6 mmol)
with a cannula at Ϫ78 ЊC under argon. The resulting mixture
was stirred at the same temperature for 12 h, poured into water
and extracted with ethyl acetate. The extracts were washed with
brine and dried over MgSO4. After the solvent had been evap-
orated under reduced pressure, the residue was separated by
PLC (chloroform) to give the vinyl sulfone 4m (151 mg, 90%) as
colourless prisms, mp 117–120 ЊC (Found: C, 74.6; H, 6.4.
C26H26O3S requires C, 74.6; H, 6.3%); νmax (NaCl)/cmϪ1 1619,
1305 and 1145; δH (400 MHz; CDCl3) 1.26–1.43 (2 H, m, CH),
1.47–1.70 (2 H, m, CH), 1.74–1.94 (3 H, m, CH), 2.17 (1 H, br
d, J 13.2, CH), 2.48 (1 H, ddd, J 3.9, 9.2 and 13.4, CH), 3.78
(1 H, s, C᎐CH), 7.53 (1 H, t, J 7.3, ArH) and 7.71 (2 H, d, J 7.3,
᎐
ArH); δC (100 MHz; CDCl3) 10.1 (q), 127.4 (d), 128.1 (d),
128.5 (d), 128.7 (d), 129.4 (d), 133.3 (d), 135.0 (d), 138.0 (s),
140.0 (s) and 143.7 (s); m/z (EI) 338 (Mϩ, 98%), 197 (96) and
102 (100).
General procedure for the reactions of alkenylselenonium salt 7b
with halides. A typical example (Table 6, entry 4): (Z)-ꢀ-bromo-
ꢁ-(phenylsulfonyl)styrene 4o
Tetrabutylammonium bromide (48 mg, 0.15 mmol) was added
to a stirred solution of diphenyl-[2-phenyl-2-(phenylsulfonyl)-
vinyl]selenonium trifluoromethanesulfonate 7b (94 mg, 0.15
mmol) in chloroform (3 cm3) at room temperature. The result-
ing mixture was stirred at the same temperature for 3 h, poured
into water and extracted with ethyl acetate. The extracts were
dried over MgSO4. After the solvent had been evaporated under
reduced pressure, the residue was separated by PLC (10:1
hexane–ethyl acetate) to give 3 (32 mg, 90%), and the vinyl
sulfone 4o (45 mg, 92%) as a colourless oil (Found: C, 52.1; H,
3.5. C14H11BrO2S requires C, 52.0; H, 3.4%); νmax (NaCl)/cmϪ1
1581, 1445, 1325 and 1151; δH (270 MHz; CDCl3) 7.02 (1 H, s,
(1 H, dt, J 4.4 and 10.7, OCH), 6.00 (1 H, s, C᎐CH), 6.79 (2 H,
᎐
d, J 7.3, ArH), 6.85 (2 H, d, J 7.3, ArH), 7.15–7.25 (6 H, m,
ArH), 7.47 (2 H, t, J 7.3, ArH), 7.59 (1 H, t, J 7.3, ArH) and
7.79 (2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 24.7 (t), 25.3 (t),
32.6 (t), 32.8 (t), 50.9 (d), 90.1 (d), 118.7 (s), 126.8 (d), 127.79
(d), 127.82 (d), 128.0 (d), 128.1 (d), 128.2 (d), 128.6 (d), 130.7
(d), 131.8 (s), 132.4 (d), 141.8 (s), 142.8 (s) and 154.9 (d);
m/z (FAB) 419 ([M ϩ H]؉, 15%), 261 (40) and 136 (67).
C᎐CH), 7.20–7.40 (5 H, m, ArH), 7.47 (2 H, t, J 7.3, ArH), 7.61
᎐
(1 H, t, J 7.3, ArH) and 7.82 (2 H, d, J 7.3, ArH); δC (100 MHz;
CDCl3) 117.2 (d), 128.3 (d), 128.8 (d), 129.5 (d), 129.9 (d), 133.7
(d), 134.0 (s), 139.7 (s) and 147.6 (s); m/z (EI) 324 (Mϩ ϩ 2,
16%), 322 (Mϩ, 17%), 181 (55), and 102 (100).
(Z)-ꢀ-[(1R,2S,5R)-Menthan-3-yloxy]-ꢁ-(phenylsulfonyl)-
styrene 4k. Colourless needles, mp 82–84 ЊC (Found: C, 72.3; H,
7.6. C24H30O3S requires C, 72.3; H, 7.6%); νmax (KBr)/cmϪ1
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247
245

View Article Online
(Z)-ꢀ-Iodo-ꢁ-(phenylsulfonyl)styrene 4n. Colourless oil
(HRMS Calc. for C14H11IO2S: M, 369.9524. Found: Mϩ,
369.9517); νmax (NaCl)/cmϪ1 1560, 1444, 1321, 1149 and 1084;
δH (400 MHz; CDCl3) 7.18 (2 H, d, J 7.3, ArH), 7.27 (2 H, t,
J 7.3, ArH), 7.35 (1 H, t, J 7.3, ArH), 7.44 (2 H, t, J 7.3,
Crystal-structure determination of 7b
C27H21F3O5S2Se, M = 625.54, monoclinic, a = 13.214(7), b =
14.200(5), c = 14.463(7) Å, β = 103.31(4)Њ, V = 2641(2) Å3,
T = 296 K, space group P21/n (#14), Z = 4, µ(MoKα) = 16.38
cmϪ1, 6577 reflections measured, 6315 unique (Rint = 0.078)
which were used in all calculations. The final wR(F2) was 0.033
(all data).†
ArH), 7.49 (1 H, s, C᎐CH), 7.59 (1 H, t, J 7.3, ArH) and 7.77
᎐
(2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 88.5 (d), 128.2 (d),
128.4 (d), 128.8 (d), 129.4 (d), 129.6 (d), 133.7 (d), 135.4 (s),
139.1 (s) and 151.7 (s); m/z (EI) 370 (Mϩ, 18%), 229 (77) and
102 (100).
† CCDC reference number 207/502. See http://www.rsc.org/suppdata/
p1/b0/b007715l for crystallographic files in .cif format.
References
(Z)-ꢀ-Chloro-ꢁ-(phenylsulfonyl)styrene 4p. Colourless oil
(HRMS Calc. for C14H11ClO2S: M, 278.0168. Found: Mϩ,
278.0162); νmax (NaCl)/cmϪ1 1580, 1420, 1321, 1149 and 1081;
δH (400 MHz; CDCl ) 6.73 (1 H, s, C᎐CH), 7.25 (2 H, d, J 7.3,
ArH), 7.34 (2 H, t, J 7.3, ArH), 7.40 (1 H, t, J 7.3, ArH), 7.48
(2 H, t, J 7.3, ArH), 7.61 (1 H, t, J 7.3, ArH) and 7.83
(2 H, d, J 7.3, ArH); δC (100 MHz; CDCl3) 128.2 (d), 128.3 (d),
128.9 (d), 129.0 (d), 129.6 (d), 130.1 (d), 132.8 (s), 133.8 (d),
140.1 (s) and 145.1 (s); m/z (EI) 278 (Mϩ, 35%), 137 (100) and
102 (83).
1 For reviews, see: (a) N. S. Simpkins, Tetrahedron, 1990, 46, 6951;
(b) P. D. Magnus, Tetrahedron, 1977, 33, 2019; (c) B. M. Trost, Bull.
Chem. Soc. Jpn., 1988, 61, 107; see also (d) O. Arjona, C. Borrallo,
F. Iradier, R. Medel and J. Plumet, Tetrahedron Lett., 1998, 39,
1977; (e) R. F. W. Jackson, D. Turner and M. H. Block, Synlett,
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2 (a) V. Farina and S. I. Hanck, J. Org. Chem., 1991, 56, 4317;
(b) M. Isobe, R. Nishizawa, T. Nishikawa and K. Yoza, Tetrahedron
Lett., 1999, 40, 6927; (c) J. Bégué, A. M’Bida, D. Bonnet-Delpon,
B. Novo and G. Resnati, Synthesis, 1996, 399; (d) M. Ochiai,
M. Kunishima, S. Tani and Y. Nagao, J. Am. Chem. Soc., 1991, 113,
3135; (e) B. L. Williamson, R. R. Tykwinski and P. J. Stang, J. Am.
Chem. Soc., 1994, 116, 93.
᎐
3
General procedure for the reactions of alkenylselenonium salt 7b
with acetylides. A typical example (Table 7, entry 1): (Z)-1,4-
diphenyl-1-(phenylsulfonyl)but-1-en-3-yne 4q
3 (a) G. E. Keck, J. H. Byers and A. M. Tafesh, J. Org. Chem., 1988,
53, 1127; (b) M. P. Gerard and N. S. Simpkins, J. Chem. Soc., Chem.
Commun., 1987, 207.
n-Butyllithium in hexane solution (1.66 mol dmϪ3) (0.22 cm3,
0.36 mmol) was added to a stirred solution of phenylacetylene
(37 mg, 0.36 mmol) in THF (3 cm3) and the solution was
strirred at 0 ЊC for 0.5 h. To the acetylenide solution thus
prepared was added a solution of diphenyl(phenylethynyl)-
selenonium trifluoromethanesulfonate 7b (188 mg, 0.3 mmol)
via cannula at Ϫ78 ЊC under argon. The resulting mixture was
stirred at the same temperature for 3 h, poured into water and
extracted with ethyl acetate. The extracts were washed with
brine and dried over MgSO4. After the solvent had been evap-
orated under reduced pressure, the residue was separated by
PLC (10:1 hexane–ethyl acetate) to give the vinyl sulfone 4q
(54 mg, 52%) as a colourless oil (HRMS Calc. for C22H16O2S:
M, 344.0871. Found: Mϩ, 344.0880); νmax (NaCl)/cmϪ1 2200,
1600, 1420, 1320 and 1150; δH (400 MHz; CDCl3) 6.44 (1 H,
4 (a) T. G. Back, S. Collins and R. G. Kerr, J. Org. Chem., 1983, 48,
3077; (b) T. G. Back, S. Collins, U. Gokhale and K. Law, J. Org.
Chem., 1983, 48, 4776; (c) T. G. Back, S. Collins and K. Law, Can. J.
Chem., 1985, 63, 2313; (d) T. G. Back, S. Collins, M. V. Krishna and
K. Law, J. Org. Chem., 1987, 52, 4258; (e) T. G. Back and M. V.
Krishna, J. Org. Chem., 1987, 52, 4265; (f ) T. G. Back, M. V.
Krishna and K. R. Muralidharan, J. Org. Chem., 1989, 54, 4146.
5 (a) V. A. Potapov, S. V. Amosova, T. N. Rakhmatulina and E. N.
Antonova, Izv. Akad. Nauk SSSR, Ser. Khim., 1988, 943; (b) Y.
Watanabe, Y. Ueno and T. Toru, Bull. Chem. Soc. Jpn., 1993, 66,
2042; (c) H. Poleschner, M. Heydenreich and U. Schilde, Liebigs
Ann., 1996, 1187; (d) T. Kataoka, Y. Banno, S. Watanabe,
T. Iwamura and H. Shimizu, Tetrahedron Lett., 1997, 38, 1809;
(e) S. Watanabe, K. Yamamoto, Y. Itagaki and T. Kataoka, J. Chem.
Soc., Perkin Trans. 1, 1999, 2053; (f ) M. Ochiai, T. Sueda, R. Noda
and M. Shiro, J. Org. Chem., 1999, 64, 8563.
6 (a) M. Ochiai, K. Oshima and Y. Masaki, Tetrahedron Lett., 1991,
32, 7711; (b) M. Ochiai, K. Oshima, Y. Masaki, M. Kunishima
and S. Tani, Tetrahedron Lett., 1993, 34, 4829; (c) M. Ochiai,
Y. Kitagawa, M. Toyonari and K. Uemura, Tetrahedron Lett., 1994,
35, 9407.
7 (a) T. Kataoka, S. Watanabe, M. Yamamoto, M. Yoshimatsu, G.
Tanabe and O. Muraoka, J. Org. Chem., 1998, 63, 6382; (b) T.
Kataoka, S. Watanabe and K. Yamamoto, Tetrahedron Lett., 1999,
40, 2153; (c) S. Watanabe, K. Yamamoto, Y. Itagaki, T. Iwamura,
T. Iwama and T. Kataoka, Tetrahedron, 2000, 56, 855.
s, C᎐CH), 7.30–7.43 (10 H, m, ArH), 7.53 (1 H, t, J 7.3, ArH),
᎐
7.59 (2 H, d, J 7.3, ArH) and 7.85 (2 H, d, J 7.3, ArH); δC (100
MHz; CDCl3) 84.8 (s), 104.2 (s), 120.5 (d), 122.3 (s), 128.0 (d),
128.2 (d), 128.5 (d), 128.8 (d), 129.3 (d), 129.6 (d), 132.1 (d),
133.4 (d), 134.1 (s), 140.5 (s) and 150.3 (s); m/z (EI) 344 (Mϩ,
40%), 202 (100) and 178 (33).
(Z)-1-Phenyl-1-(phenylsulfonyl)oct-1-en-3-yne 4r. Colourless
oil (HRMS Calc. for C20H20O2S: M, 324.1184. Found: Mϩ,
324.1181); νmax (NaCl)/cmϪ1 2210, 1590, 1450, 1320 and 1150;
δH (400 MHz; CDCl3) 0.95 (3 H, t, J 7.0, CH3), 1.43–1.63 (4 H,
8 T. Kataoka, S. Watanabe and K. Yamamoto, Tetrahedron Lett.,
1999, 40, 931.
9 S. Watanabe, E. Mori, H. Nagai and T. Kataoka, Synlett, 2000, 49.
10 R. J. Cremlyn, An Introduction to Organosulfur Chemistry, Wiley,
Chichester, 1996.
᎐
m, CH ), 2.47 (2 H, dt, J 2.4 and 7.0, C᎐CCH ), 6.23 (1 H, t,
᎐
2
2
11 (a) P. J. Stang, T. Kitamura, M. Boeshar and H. Wingert, J. Am.
Chem. Soc., 1989, 111, 2225; (b) J. S. Lodaya and G. F. Koser, J. Org.
Chem., 1990, 55, 1513.
12 (a) M. S. Newman and T. B. Patrick, J. Am. Chem. Soc., 1970, 92,
4312; (b) P. J. Stang, M. G. Mangum, D. P. Fox and P. Haak, J. Am.
Chem. Soc., 1974, 96, 4562; (c) T. Kitamura and P. J. Stang,
Tetrahedron Lett., 1988, 29, 1887.
J 2.4, C᎐CH), 7.29–7.37 (5 H, m, ArH), 7.44 (2 H, t, J 7.3,
᎐
ArH), 7.56 (1 H, t, J 7.3, ArH) and 7.83 (2 H, d, J 7.3, ArH);
δC (100 MHz; CDCl3) 13.6 (q), 20.0 (t), 22.0 (t), 30.2 (t), 76.1 (s),
107.7 (s), 121.7 (d), 128.0 (d), 128.2 (d), 128.7 (d), 129.2 (d),
129.6 (d), 133.3 (d), 134.3 (s), 140.8 (s) and 149.6 (s); m/z (EI)
324 (Mϩ, 2%), 141 (67) and 97 (100).
13 (a) J. L. Dicktein and S. I. Miller, The Chemistry of the Carbon-
Carbon Triple Bond Part 2. ed. S. Patai, Wiley, New York, 1978;
(b) K. N. Houk, R. W. Strozier, M. D. Rozeboom and S. J. Nagase,
J. Am. Chem. Soc., 1982, 104, 323.
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J. Organomet. Chem., 1977, 135, 91; (b) M. Ochiai, K. Sumi, Y.
Takaoka, M. Kunishima, Y. Nagao, M. Shiro and E. Fujita,
Tetrahedron, 1988, 44, 4095; (c) J. A. McCullough and G.
Hamburger, J. Am. Chem. Soc., 1942, 64, 508; (d) J. D. McCullough
and R. E. Marsh, J. Am. Chem. Soc., 1950, 72, 4556; (e) H. Fujihara,
H. Miwa, M. Ikemori and N. Furukawa, J. Am. Chem. Soc., 1991,
113, 6337; (f ) T. Takahashi, N. Kurose, S. Kawanami, Y. Arai and
T. Koizumi, J. Org. Chem., 1994, 59, 3262.
(Z)-5,5-Dimethyl-1-phenyl-1-(phenylsulfonyl)hex-1-en-3-yne
4s. Colourless oil (HRMS Calc. for C20H20O2S: M, 324.1184.
Found: Mϩ, 324.1190); νmax (NaCl)/cmϪ1 2210, 1590, 1450, 1330
and 1160; δH (400 MHz; CDCl3) 1.34 (9 H, s, CH3), 6.23 (1 H, s,
C᎐CH), 7.29–7.38 (5 H, m, ArH), 7.44 (2 H, t, J 7.3, ArH), 7.56
᎐
(1 H, t, J 7.3, ArH) and 7.84 (2 H, d, J 7.3, ArH); δC (100 MHz;
CDCl3) 29.3 (s), 30.9 (q), 75.6 (s), 115.4 (s), 122.5 (d), 128.4 (d),
128.7 (d), 129.2 (d), 129.7 (d), 130.2 (d), 133.8 (s), 135.0 (s),
141.5 (s) and 150.0 (s); m/z (EI) 324 (Mϩ, 70%), 183 (35), 167
(35) and 97 (100).
246
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247

View Article Online
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4857.
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7373; (b) P. Nebois and A. E. Greene, J. Org. Chem., 1996, 61, 5210;
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·
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17 Z. Rappoport, Acc. Chem. Res., 1981, 14, 7.
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417.
J. Chem. Soc., Perkin Trans. 1, 2001, 239–247
247