Heck vinylations using vinyl sulfide, vinyl sulfoxide, vinyl sulfone, or vinyl sulfonate derivatives and aryl bromides catalyzed by a palladium complex derived from a tetraphosphine

Article abstract of DOI:10.1055/s-2006-950244

The adverse impact of sulfur compounds on catalytic performance is well known. The tetraphosphine cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphino) methyl]cyclopentane in combination with allylchloropalladium dimer affords an efficient catalyst for the Hec

Full text of DOI:10.1055/s-2006-950244

PAPER
3495
Heck Vinylations Using Vinyl Sulfide, Vinyl Sulfoxide, Vinyl Sulfone, or Vinyl
Sulfonate Derivatives and Aryl Bromides Catalyzed by a Palladium Complex
Derived from a Tetraphosphine
Heck
Vinylations
C
atalyzed by
m
a
P
alladium Compl
e
ex
D
erived
d
from
a
T
etraphosp
B
hine attace,a Touriya Zair,b Henri Doucet,*a Maurice Santelli*a
a
UMR 6180 CNRS and Université d'Aix-Marseille III: ‘Chirotechnologies : catalyse et biocatalyse’, Laboratoire de Synthèse Organique,
Faculté des Sciences de Saint Jérôme, Université d'Aix-Marseille III, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20,
France
Fax +33(4)91983865; E-mail: henri.doucet@univ-cezanne.fr; E-mail: m.santelli@univ-cezanne.fr
b
Laboratoire de Chimie Organique Appliquée, Faculté des Sciences, Université Moulay Ismail, BP 4010, Beni M’mhammed,
50000 Meknes, Morocco
Received 7 June 2006; revised 28 June 2006
reaction with phenyl vinyl sulfide using 6 mol% of lithi-
um tetrachloropalladate(II) as catalyst required the addi-
tion of one equivalent of the thiophilic agent
phenylmercury chloride and one equivalent of copper(II)
Abstract: The adverse impact of sulfur compounds on catalytic
performance is well known. The tetraphosphine cis,cis,cis-1,2,3,4-
tetrakis[(diphenylphosphino)methyl]cyclopentane in combination
with allylchloropalladium dimer affords an efficient catalyst for the
Heck reaction of sulfur-containing alkenes with aryl bromides. The chloride. Using this mixture, [2-(phenylsulfanyl)vi-
rates and yields of the reactions strongly depend on the oxidation
nyl]benzene was obtained in 68% yield as an Z/E mixture
(ratio 3:7).5 Recently, Itami, Yoshida et al have reported
state of the sulfur atom. Using vinyl sulfides with 1 mol% catalyst,
low to moderate yields of arylated alkenes were obtained. Phenyl
the efficient Heck vinylation of aryl iodides using pyr-
vinyl sulfoxide was found to be more reactive, and satisfactory
imid-2-yl vinyl sulfide as the alkene with 5 mol% of
bis(tri-tert-butylphosphine)palladium as the catalyst. The
yields of (E)-[2-(phenylsulfinyl)vinyl]benzene derivatives were ob-
tained using 1 mol% catalyst. With methyl vinyl sulfone, very high
pyrimid-2-yl group on sulfur greatly enhances the reactiv-
ity of vinyl sulfides in the Heck reaction.6a To our knowl-
edge there are only a few examples of Heck reaction using
vinyl sulfoxides in the literature and this reflects the low
reactivity of such substrates.7 Moreover, these reactions
were generally performed using reactive but expensive
aryl iodides and in some cases with silver carbonate as the
base. For example, Carretero et al. have described the re-
action of 1,2-disubstituted vinyl sulfoxides with aryl io-
dides using palladium(II) acetate (10 mol%) associated
with 1,1¢-bis(diphenylphosphino)ferrocene (10 mol%) as
the catalyst and silver carbonate (200 mol%) as the
base.7c,e Heck reactions using vinyl sulfonamides,8 vinyl
sulfones,9–11 and vinylsulfonates12 have also been de-
scribed. In general the reactions with vinyl sulfonamides
were performed using 2–5 mol% of tetrakis(triphen-
ylphosphine)palladium(0) or palladium(II) acetate associ-
ated with triphenylphosphine.8 The synthesis of b-
arylvinyl sulfones in 20–74% yields by Heck arylation of
phenyl vinyl sulfone using palladium(II) acetate (5 mol%)
associated with tri-2-tolylphosphine (10–22 mol%) has
also been reported recently.9 The reaction of phenyl vinyl
sulfone with an aryl iodide using palladium(II) acetate (25
mol%) without the addition of a ligand also proceeds in
good yield.10 In addition, it has been reported that PEG
resin-supported catalyst (10 mol%) catalyzes the reaction
of iodobenzene with phenyl vinyl sulfone.11 Finally, ethyl
vinylsulfonate has been arylated using palladium(II) ace-
tate associated with tri-2-tolylphosphine.12
yields of (E)-[2-(methylsulfonyl)vinyl]benzene derivatives were
obtained using 1–0.1 mol% catalyst. Phenyl vinyl sulfone and phen-
yl vinylsulfonate also gave high yields of the expected products, but
in the presence of 0.4–1 mol% catalyst.
Key words: Heck reaction, palladium, phosphine, vinylsulfur, cat-
alyst
Over the last thirty year, the arylation of alkenes such as
acrylates, styrenes, and enol ethers catalyzed by palladi-
um has undergone an outstanding level of development1–4
However, despite the rich chemistry of organosulfur com-
pounds, palladium-catalyzed Heck vinylation using sul-
fur-containing alkenes remains worthy of study, since
sulfur-containing compounds have long been known to
act as palladium-catalyst poisons because of their coordi-
nating properties that often rendered these catalytic reac-
tions totally ineffective. It appears that sulfur species bond
very strongly to the active site of the palladium catalysts
forming stable metal–sulfide complexes and thereby pre-
venting the reactants from coordinating. The sulfur atom
can adopt several different oxidation states, thus enhanc-
ing the versatility of molecules containing sulfur function-
alities. The reactivity of vinyl sulfides, vinyl sulfoxides,
and vinyl sulfones in the Heck reaction is very different.
Vinyl sulfides and vinyl sulfoxides act as strong catalyst
poisons. Very few examples of reactions using vinyl sul-
fides have been reported so far.5,6 Attempts to effect the
While monophosphine and diphosphine ligands have
been successfully used for the Heck reaction of some
sulfur-containing alkenes, the efficiency of polydentate
SYNTHESIS 2006, No. 20, pp 3495–3505
1
7.
1
0
.
2
0
0
6
Advanced online publication: 10.10.2006
DOI: 10.1055/s-2006-950244; Art ID: Z11506SS
© Georg Thieme Verlag Stuttgart · New York

3496
A. Battace et al.
PAPER
Ph2P
Ph2P
ligands such as tetraphosphines has not been examined.
Moreover, the reactivity of aryl bromides with such alk-
enes has attracted less attention than the reactivity of aryl
iodides. Thus, an effective and selective method for the
reaction of sulfur-containing alkenes, especially aryl bro-
mides, is still a suitable subject for significant improve-
ment.
PPh2
PPh2
Tedicyp
Figure 1
activity of these substrates toward Heck vinylation, we
began by exploring the reaction of ethyl vinyl sulfide with
4-bromoacetophenone (Scheme 1, Table 1). The reac-
tions were performed at 130 °C, under argon in the pres-
ence of a 1:2 ratio of allylchloropalladium dimer/Tedicyp
as catalyst. After extensive screening of the reaction con-
ditions, we found that the most suitable base appears to be
sodium acetate. Bases such as potassium carbonate, sodi-
um carbonate, and sodium hydrogen carbonate using N,N-
dimethylformamide as solvent gave unreacted 4-bro-
moacetophenone (Table 1, entries 1–3). On the other
hand, using sodium acetate with N,N-dimethylformamide
gave 1 in 20% yield. Next we examined the influence of
the solvent on the yield of this reaction. Using N-methyl-
2-pyrrolidinone or xylene gave no vinylation product
(Table 1, entries 5 and 6). The best results were obtained
using N,N-dimethylacetamide (DMAC) in combination
with sodium acetate (Table 1, entry 7). Using these condi-
tions, 1 was obtained in 28% isolated yield. It should be
noted that this reaction is regio- and stereoselective in fa-
vor of the E isomer.
In order to obtain a highly stable palladium catalyst, we
have prepared the tetraphosphine ligand, cis,cis,cis-
1,2,3,4-tetrakis[(diphenylphosphino)methyl]cyclopentane13
(Tedicyp, Figure 1). The idea of the design of this ligand
was that intermediate palladium(0) species have to be pro-
tected by internal ligation against possible decomposition
pathways through underligation and subsequent colloid
formation. The presence of this polydentate ligand on pal-
ladium might also reduce the poisoning of the catalyst or
reverse this poisoning process when strongly coordinating
substrates such as sulfur-containing alkenes are used. We
have already reported the results obtained in allylic substi-
tution,13 in the Suzuki cross-coupling reaction,14 and in
the Sonogashira reaction15 using Tedicyp as the ligand.
We have also described several results obtained for the
Heck reaction.16,17 For example, we have reported the re-
action with butyl acrylate,16,17a alkenols17e–g enol
ethers,17b,h and vinylsilanes17i with a variety of aryl bro-
mides. In order to further establish the requirement for
successful Heck vinylation with our catalyst, we describe
here the synthesis of 2-arylvinyl sulfides, sulfoxides, sul-
fones, and sulfonates by highly regio- and stereoselective
arylations of vinylsulfur derivatives using the palladium/
Tedicyp catalyst.
[PdCl(CH2CH=CH2)]2/
Tedicyp (1:2)
X
S
R
R
+
130 °C
S
1–6
R = MeCO, PhCO, HCO, CN, Me, H
Since there are only a few examples of Heck vinylation
using vinyl sulfides in the literature, reflecting the low re-
Scheme 1
Table 1 Palladium-Catalyzed Coupling of Aryl Halides with Ethyl Vinyl Sulfide (Scheme 1)a
Entry
1
Aryl halide
Solvent
DMF
Base
Product
R
Yield (%)
4-bromoacetophenone
4-bromoacetophenone
4-bromoacetophenone
4-bromoacetophenone
4-bromoacetophenone
4-bromoacetophenone
4-bromoacetophenone
4-bromobenzophenone
4-bromobenzaldehyde
4-bromobenzonitrile
3-bromotoluene
K2CO3
Na2CO3
NaHCO3
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
1
1
1
1
1
1
1
2
3
4
5
6
4-C(O)Me
4-C(O)Me
4-C(O)Me
4-C(O)Me
4-C(O)Me
4-C(O)Me
4-C(O)Me
4-C(O)Ph
4-CHO
0
0
2
DMF
3
DMF
0
4
DMF
20
0
5
NMP
6
xylene
DMAC
DMAC
DMAC
DMAC
DMAC
DMAC
0
7
28
53
24
36
12b
11b
8
9
10
11
12
4-CN
3-Me
iodobenzene
H
a Conditions: [PdCl(CH2CH=CH2)]2/Tedicyp (1:2) (0.01 mmol), aryl halide (1 mmol), ethyl vinyl sulfide (2 mmol), base (2 mmol), 130 °C,
20 h, argon, isolated yields.
b This compound was not obtained in pure form.
Synthesis 2006, No. 20, 3495–3505 © Thieme Stuttgart · New York

PAPER
Heck Vinylations Catalyzed by a Palladium Complex Derived from a Tetraphosphine
3497
After this optimization of the reaction conditions, we per-
formed vinylation on a variety of aryl bromides. Higher
reactions rates were observed with electron-poor aryl bro-
mides. The vinylation of 4-bromobenzophenone, 4-bro-
mobenzaldehyde, and 4-bromobenzonitrile gave the
corresponding (E)-[2-(ethylsulfanyl)vinyl]benzene deriv-
atives 2–4 in 24–53% yield (Table 1, entries 8–10). On the
other hand, using 3-bromotoluene and iodobenzene, the
products 5 and 6 were obtained in very low yields together
with unidentified products (Table 1, entries 11 and 12).
O
S
X
[PdCl(CH2CH=CH2)]2/
Tedicyp (1:2)
R
Ph
R
+
O
S
NaOAc, DMAC, 130 °C
13–18
Ph
R = MeCO, PhCO, CN, CF3, H
Scheme 3
Table 3 Palladium-Catalyzed Coupling of Aryl Halides with
Phenyl Vinyl Sulfoxide (Scheme 3)a
Next, we investigated this reaction in the presence of
phenyl vinyl sulfide (Scheme 2, Table 2). With this al-
kene we obtained quite similar results to those obtained
with ethyl vinyl sulfide. Using the electron-deficient aryl
bromides 4-bromoacetophenone, 4-bromobenzophenone,
and 4-bromobenzonitrile, the (E)-[2-(phenylsulfanyl)vi-
nyl]benzene derivatives 7, 8, and 10 were obtained in 42–
48% isolated yields (Table 2, entries 1, 2, and 4). 4-Bro-
mobenzaldehyde and 1-bromo-4-fluorobenzene gave the
arylation products in lower yields. Using this alkene, the
best yield (55%) was obtained using iodobenzene
(Table 2, entry 6). Again, the arylation using phenyl vinyl
sulfide is fully regio- and stereocontrolled in favor of the
E isomer.
Entry Aryl halide
Product R
Yield
(%)
1
2
3
4
4-bromoacetophenone
13
14
15
16
4-C(O)Me
57
60
62
55
4-bromobenzophenone
4-bromobenzonitrile
4-C(O)Ph
4-CN
1-bromo-4-
(trifluoromethyl)benzene
4-CF3
5
6
iodobenzene
17
18
H
65
1-bromonaphthalene
2,3-(CH=CH)2 65
a Conditions: [PdCl(CH2CH=CH2)]2/Tedicyp (1:2) (0.01 mmol), aryl
halide (1 mmol), phenyl vinyl sulfoxide (2 mmol), NaOAc (2 mmol),
DMAC, 130 °C, 20 h, argon, isolated yields.
[PdCl(CH2CH=CH2)]2/
Tedicyp (1:2)
X
S
R
Ph
lated yields using 1 mol% catalyst. When higher ratios
substrates/catalyst were used, low conversions of the aryl
halides were observed.
R
+
NaOAc, DMAC, 130 °C
S
Ph
7–12
R = MeCO, PhCO, HCO, CN, F, H
Then, we examined the reactivity of methyl vinyl sulfone
towards a wide variety of aryl halides (Scheme 4,
Table 4). We were very pleased to find that, with this alk-
ene, very high yields of (E)-[2-(methylsulfonyl)vi-
nyl]benzene derivatives 19–43 were obtained in all cases
by using 1–0.1 mol% catalyst. Electron-deficient para-
substituted aryl bromides such as 4-bromobenzophenone,
methyl 4-bromobenzoate, 4-bromobenzonitrile, and 1-
bromo-4-(trifluoromethyl) benzene gave regio- and stereo-
selectively the vinylation products 20–25 in 88–94% iso-
lated yields using 0.1 mol% catalyst (Table 4, entries 2–
7). The electron-rich aryl bromides 4-bromotoluene, 1-
bromo-4-tert-butylbenzene, and 4-bromoanisole were
also reacted successfully using 0.1 mol% catalyst
(Table 4, entries 9–11). These results indicate that the ox-
idative addition of the aryl bromide to palladium is not the
rate-limiting step of the catalytic cycle when methyl vinyl
sulfone is used as the alkene. As expected, the reactivity
of the meta-substituted aryl bromides, 3-bromoacetophe-
none, 3-bromobenzaldehyde, and 1-bromo-3,5-bis(trifluo-
romethyl)benzene was found to be very similar (Table 4,
entries 12–14). On the other hand, the reactions of ortho-
Scheme 2
Table 2 Palladium-Catalyzed Coupling of Aryl Halides with
Phenyl Vinyl Sulfide (Scheme 2)a
Entry Aryl Halide
Product R
Yield
(%)
1
2
3
4
5
6
4-bromoacetophenone
7
8
4-C(O)Me
45
4-bromobenzophenone
4-bromobenzaldehyde
4-bromobenzonitrile
1-bromo-4-fluorobenzene
iodobenzene
4-C(O)Ph
4-CHO
4-CN
4-F
42
9
20b
48
10
11
12
15b
55
H
a Conditions: [PdCl(CH2CH=CH2)]2/Tedicyp (1:2) (0.01 mmol), aryl
halide (1 mmol), phenyl vinyl sulfide (2 mmol), NaOAc (2 mmol),
DMAC, 130 °C, 20 h, argon, isolated yields.
b This compound was not obtained in pure form.
The reaction using phenyl vinyl sulfoxide with aryl ha- substituted aryl bromides 2-bromobenzonitrile and 2-bro-
lides was more successful (Scheme 3, Table 3). We have moanisole had to be performed with 0.4–1 mol% catalyst
investigated this reaction using four electron-poor aryl in order to obtain high yields of vinylation products 33
bromides, and also with iodobenzene and 1-bromonaph- and 35 (Table 4, entries 15 and 17). The reaction using the
thalene. In all cases, the b-arylated compounds 13–18 ortho- or di-ortho-substituted aryl bromides 1-bro-
were regio- and stereoselectively obtained in 55–65% iso- monaphthalene, 1-bromo-2,4,6-trimethylbenzene, and 9-
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3498
A. Battace et al.
PAPER
bromoanthracene proceeds nicely using 0.1 mol% catalyst
(Table 4, entries 16, 18–20). Even the sterically very con-
gested 1-bromo-2,4,6-triisopropylbenzene gave the ex-
pected product 38 using 1 mol% of this catalytic system
(Table 4, entry 21). Finally, we performed a few reactions
using hetaryl bromides. With this catalyst electron-poor
heteroaromatics such as 3- and 4-bromopyridines and 4-
bromoisoquinoline and the electron-rich substrate 2-bro-
mothiophene led to the expected products 39–43 in good
yields. Both these electron-poor and electron-rich hetaryl
bromides have been reacted using substrate/catalyst ratios
of 1000 (Table 4, entries 22–26).
O
S
Ar
X
[PdCl(CH2CH=CH2)]2/
Tedicyp (1:2)
+
Ar
Me
O
O
S
NaOAc, DMAC, 130 °C
19–43
Me
O
R = MeCO, PhCO, HCO, CO2Me, CN, CF3, F, Me, i-Pr, t-Bu, OMe
Scheme 4
Phenyl vinyl sulfone was found to be less reactive than
methyl vinyl sulfone by a factor of ten (Scheme 5,
Table 5). The expected 2-arylated phenyl vinyl sulfones
Table 4 Palladium-Catalyzed Coupling of Aryl Halides with Methyl Vinyl Sulfone (Scheme 4)a
Entry Aryl bromide Ratio substrate/catalyst Product
Ar
Yield (%)
92
1
2
iodobenzene
1000
1000
1000
1000
1000
1000
1000
250
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
36
37
38
39
40
41
42
43
Ph
4-bromoacetophenone
4-bromobenzophenone
4-bromobenzaldehyde
methyl 4-bromobenzoate
4-bromobenzonitrile
4-Me(O)CC6H4
4-Ph(O)CC6H4
4-OHCC6H4
4-MeO2CC6H4
4-NCC6H4
4-F3CC6H4
4-FC6H4
93
3
92
4
90
5
88
6
93
7
1-bromo-4-(trifluoromethyl)benzene
1-bromo-4-fluorobenzene
4-bromotoluene
94
8
96
9
1000
1000
1000
1000
250
4-MeC6H4
4-t-BuC6H4
4-MeOC6H4
3-Me(O)CC6H4
3-OHCC6H4
3,5-(F3C)2C6H3
2-NCC6H4
1-naphthyl
2-MeOC6H4
2,4,6-Me3C6H2
2,4,6-Me3C6H2
9-anthryl
90
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
1-bromo-4-tert-butylbenzene
4-bromoanisole
92
95
3-bromoacetophenone
3-bromobenzaldehyde
1-bromo-3,5-bis(trifluoromethyl)benzene
2-bromobenzonitrile
94
93
1000
250
83
88
1-bromonaphthalene
1000
100
94
2-bromoanisole
80
1-bromo-2,4,6-trimethylbenzene
1-bromo-2,4,6-trimethylbenzene
9-bromoanthracene
250
92
1000
1000
100
77b
90
1-bromo-2,4,6-triisopropylbenzene
3-bromopyridine
2,4,6-i-Pr3C6H2
3-pyridyl
84
1000
1000
1000
1000
1000
90
4-bromopyridine
4-pyridyl
91
3-bromoquinoline
3-quinolyl
91
4-bromoisoquinoline
4-isoquinolyl
2-thienyl
89
2-bromothiophene
87
a Conditions: [PdCl(CH2CH=CH2)]2/Tedicyp (1:2), aryl halide (1 mmol), methyl vinyl sulfone (2 mmol), NaOAc (2 mmol), DMAC, 130 °C,
20 h, argon, isolated yields.
b GC yield.
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Heck Vinylations Catalyzed by a Palladium Complex Derived from a Tetraphosphine
3499
Table 5 Palladium-Catalyzed Coupling of Aryl Bromides with Phenyl Vinyl Sulfone (Scheme 5)a
Entry
1
Aryl bromide
Ratio substrate/catalyst Product
R
Yield (%)
92
4-bromoacetophenone
4-bromoacetophenone
4-bromobenzophenone
4-bromobenzaldehyde
4-bromobenzonitrile
1-bromo-4-(trifluoromethyl)benzene
1-bromo-4-(trifluoromethyl)benzene
1-bromo-4-fluorobenzene
4-bromotoluene
100
1000
100
100
100
100
250
100
100
100
100
100
44
44
45
46
47
48
48
49
50
51
52
53
4-C(O)Me
4-C(O)Me
4-C(O)Ph
4-CHO
4-CN
2
24b
88
3
4
88
5
45
6
4-CF3
85
7
4-CF3
76b
93
8
4-F
9
4-Me
90
10
11
12
4-bromoanisole
4-OMe
2,3-(CH=CH)2
2-Me
71
1-bromonaphthalene
2-bromotoluene
65
50
a Conditions: [PdCl(CH2CH=CH2)]2/Tedicyp (1:2), aryl bromide (1 mmol), phenyl vinyl sulfone (2 mmol), NaOAc (2 mmol), DMAC, 130 °C,
20 h, argon, isolated yields.
b GC yield.
44–53 were generally obtained in good yields, but 1 mol%
O
O
Br
catalyst had to be used in order to obtain high conversions
of the aryl bromides. Quite similar yields were obtained
with electron-poor and electron-rich aryl bromides such
as 4-bromobenzophenone, 1-bromo-4-fluorobenzene, and
4-bromotoluene indicating again that the oxidative addi-
tion of the aryl bromides to palladium is not the rate-lim-
iting step of the reactions (Table 5, entries 1–10). Lower
yields were obtained using the sterically hindered sub-
strates 2-bromotoluene and 1-bromonaphthalene
(Table 5, entries 11 and 12).
[PdCl(CH2CH=CH2)]2/
Tedicyp (1:2)
S
R
Ph
+
R
NaOAc, DMAC, 130 °C
O
O
S
44–53
Ph
R = MeCO, PhCO, HCO, CN, CF3, F, OMe, MeCN, OMe
Scheme 5
O
S
Br
[PdCl(CH2CH=CH2)]2/
Tedicyp (1:2)
OPh
R
R
O
+
O
S
Finally, we reacted phenyl vinylsulfonate with three aryl
bromides (Scheme 6, Table 6). Satisfactory yields of
products 54–56 were obtained with 4-bromobenzonitrile,
4-bromoanisole, and 1-bromonaphthalene using 0.4
mol% catalyst. Low to medium yields were obtained us-
ing 0.1 mol% catalyst. Again, the E isomers were regio-
and stereoselectively obtained.
NaOAc, DMAC, 130 °C
OPh
54–57
O
R = CN, OMe
Scheme 6
Table 6 Palladium-Catalyzed Coupling of Aryl Bromides with Phenyl Vinyl Sulfonate (Scheme 6)a
Entry
Aryl bromide
Ratio substrate/catalyst
Product
54
R
Yield (%)
1
2
3
4
5
6
4-bromobenzonitrile
4-bromobenzonitrile
4-bromoanisole
250
1000
250
4-CN
4-CN
4-OMe
4-OMe
88
54
(66)b
86
55
4-bromoanisole
1000
250
55
50b
85
1-bromonaphthalene
1-bromonaphthalene
56
2,3-(CH=CH)2
2,3-(CH=CH)2
1000
56
8b
a Conditions: [PdCl(CH2CH=CH2)]2/Tedicyp (1:2), aryl bromide (1 mmol), phenyl vinyl sulfonate (2 mmol), NaOAc (2 mmol), DMAC,
130 °C, 20 h, argon, isolated yields.
b GC yields.
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A. Battace et al.
PAPER
Palladium–Tedicyp Catalyst13
In summary, in the presence of the palladium–Tedicyp
complex, the Heck reaction of various aryl bromides with
sulfur-containing alkenes gives selective access to the
corresponding b-arylated vinylsulfur derivatives. The ox-
idation state of the sulfur atom plays a key role in Heck vi-
nylation, as vinyl sulfides and vinyl sulfoxides act as
strong catalyst poisons. Using vinyl sulfides with 1 mol%
catalyst, low to moderate yields of arylated alkenes were
obtained, however, this reaction was regio- and stereose-
lective in favor of E isomers. Phenyl vinyl sulfoxide was
more reactive than vinyl sulfides, and satisfactory yields
of (E)-[2-(phenylsulfinyl)vinyl]benzene derivatives were
obtained with a variety of aryl bromides using 1 mol%
An oven-dried 40-mL Schlenk tube equipped with a magnetic stir-
ring bar, under argon atmosphere, was charged with [PdCl(h3-
CH2CH=CH2)]2 (4.2 mg, 11.6 mmol) and Tedicyp (20 mg, 23.2
mmol). Anhyd DMF (2.5 mL) was added, then the soln was stirred
at r.t. for 10 min.
2-(Arylvinyl)sulfur Derivatives; General Procedure
Typically, aryl halide (1 mmol), alkene (2 mmol), and NaOAc
(0.164 g, 2 mmol) in DMAC (3 mL) in the presence of
[PdCl(CH2CH=CH2)]2–cis,cis,cis-1,2,3,4-tetrakis[(diphenylphos-
phino)methyl]cyclopentane 1:2 complex under argon was heated to
130 °C for 20 h. The corresponding products or a mixture of prod-
ucts were obtained after addition of H2O (20 mL), extraction with
CH2Cl2 (20 mL), separation, drying (MgSO4), evaporation, and pu-
catalyst. We also studied the reactivity of methyl vinyl rification by chromatography (silica gel, pentane–Et2O).
sulfone with several aryl halides. With this alkene, very
(E)-4-[2-(Ethylsulfanyl)vinyl]acetophenone (1)
high yields of E-[2-(methylsulfonyl)vinyl]benzene deriv-
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and ethyl
atives were obtained in all cases by using 1–0.1 mol% cat-
alyst. Both electron-rich and electron-deficient para-
vinyl sulfide (0.176 g, 2 mmol) afforded 1; yield: 0.058 g (28%).
1H NMR (300 MHz, CDCl3): d = 7.88 (d, J = 8.5 Hz, 2 H), 7.33 (d,
substituted aryl bromides were reacted successfully using
J = 8.5 Hz, 2 H), 6.92 (d, J = 15.7 Hz, 1 H), 6.44 (d, J = 15.7 Hz, 1
0.1 mol% catalyst. These results indicate that the oxida-
tive addition of the aryl bromide to palladium is probably
H), 2.87 (s, 3 H), 2.86 (q, J = 7.4 Hz, 2 H), 1.37 (t, J = 7.4 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 197.4, 141.7, 135.1, 129.1, 128.9,
not the rate-limiting step of the catalytic cycle when
methyl vinyl sulfone is used as the alkene. For this reason,
125.2, 124.7, 26.5, 26.4, 14.4.
Anal. Calcd for C12H14OS: C, 69.86; H, 6.84. Found: C, 69.74; H,
6.99.
this method is applicable to both electron-deficient and
electron-rich aryl bromides. This reaction also proceeds
nicely using sterically hindered aryl bromides. Even the
(E)-4-[2-(Ethylsulfanyl)vinyl]benzophenone (2)
sterically very congested 1-bromo-2,4,6-triisopropylben-
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and ethyl
zene gave the expected arylated alkene. Finally, phenyl
vinyl sulfone and phenyl vinylsulfonate also generally
gave high yields of the expected products, but it was nec-
essary to use 0.4–1 mol% of catalyst. In all cases the reac-
tion with vinylsulfur-containing derivatives gave regio-
and stereoselectively the [(E)-2-arylvinyl]sulfur deriva-
tives. It should be noted that several reactions could be
performed with as little as 0.1–0.4% catalyst. With these
sulfur-containing alkenes, the presence of the four phos-
phines close to the palladium center might reduce the poi-
soning of the catalyst or reverse this poisoning process.
We believe that this system compares favorably with oth-
er catalyst systems that have been reported for reactions
using vinylsulfur derivatives. Moreover, several sulfur-
containing alkenes are commercially available. This is a
practical advantage of this reaction.
vinyl sulfide (0.176 g, 2 mmol) afforded 2; yield: 0.142 g (53%).
1H NMR (300 MHz, CDCl3): d = 7.82–7.70 (m, 4 H), 7.56 (t,
J = 8.5 Hz, 1 H), 7.48 (t, J = 8.5 Hz, 2 H), 7.37 (d, J = 8.5 Hz, 2 H),
6.93 (d, J = 15.7 Hz, 1 H), 6.46 (d, J = 15.7 Hz, 1 H), 2.86 (q,
J = 7.4 Hz, 2 H), 1.37 (t, J = 7.4 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 196.0, 141.2, 137.9, 135.4, 132.1,
130.8, 129.8, 128.9, 128.3, 125.0, 124.8, 26.4, 14.4.
Anal. Calcd for C17H16OS: C, 76.08; H, 6.01. Found: C, 76.24; H,
5.80.
(E)-4-[2-(Ethylsulfanyl)vinyl]benzaldehyde (3)
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and ethyl
vinyl sulfide (0.176 g, 2 mmol) afforded 3; yield: 0.046 g (24%).
1H NMR (300 MHz, CDCl3): d = 9.93 (s, 1 H), 7.80 (d, J = 8.5 Hz,
2 H), 7.39 (d, J = 8.5 Hz, 2 H), 6.96 (d, J = 15.7 Hz, 1 H), 6.44 (d,
J = 15.7 Hz, 1 H), 2.85 (q, J = 7.4 Hz, 2 H), 1.37 (t, J = 7.4 Hz, 3
H).
13C NMR (75 MHz, CDCl3): d = 191.6, 143.0, 130.3, 130.1, 130.0,
125.6, 124.4, 26.4, 14.4.
DMAC analytical grade (99%) was not distilled before use. NaOAc
99% was used. Aryl halides and alkenes were used without purifi-
cation. All reactions were run under argon using vacuum lines in
Schlenk tubes in oven-dried glassware. The reactions were followed
by GC and NMR for high-boiling-point substrates and by GC for
low-boiling-point substrates. 1H (300 MHz) and 13C (75 MHz) spec-
tra were recorded in CDCl3 relative to CDCl3. Flash chromatogra-
phy was performed on silica gel (230–400 mesh).
Anal. Calcd for C11H12OS: C, 68.71; H, 6.29. Found: C, 68.87; H,
6.41.
(E)-4-[2-(Ethylsulfanyl)vinyl]benzonitrile (4)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and ethyl vi-
nyl sulfide (0.176 g, 2 mmol) afforded 4; yield: 0.068 g (36%).
1H NMR (300 MHz, CDCl3): d = 7.55 (d, J = 8.5 Hz, 2 H), 7.34 (d,
J = 8.5 Hz, 2 H), 6.93 (d, J = 15.6 Hz, 1 H), 6.38 (d, J = 15.6 Hz, 1
H), 2.86 (q, J = 7.4 Hz, 2 H), 1.37 (t, J = 7.4 Hz, 3 H).
CAS Registry No.: 5, 214118-06-6; 6, 0-80-6; 11, 229467-68-9; 12,
7214-53-1; 17, 40110-66-5; 19, 15436-11-0; 23, 115665-91-3; 24,
69957-44-4; 25, 115665-90-2; 26, 69957-46-6; 27, 69957-45-5; 29,
56069-43-3; 39, 68063-71-8; 40, 68063-72-9; 43, 68063-73-0; 44,
721427-01-6; 47, 125951-06-6; 48, 855298-16-7; 49, 106492-30-2;
50, 30166-88-2; 51, 87891-80-3; 52, 56361-22-9; 53, 56361-21-8.
13C NMR (75 MHz, CDCl3): d = 141.2, 132.5, 130.4, 125.6, 123.7,
119.1, 109.5, 26.4, 14.3.
Anal. Calcd for C11H11NS: C, 69.80; H, 5.86. Found: C, 69.61; H,
5.98.
Synthesis 2006, No. 20, 3495–3505 © Thieme Stuttgart · New York

PAPER
Heck Vinylations Catalyzed by a Palladium Complex Derived from a Tetraphosphine
3501
(E)-3-[2-(Ethylsulfanyl)vinyl]toluene (5)
The reaction of 3-bromotoluene (0.171 g, 1 mmol) and ethyl vinyl
sulfide (0.176 g, 2 mmol) afforded 5; yield: 0.021 g (12%).
(E)-[2-(Phenylsulfanyl)vinyl]benzene (12)
The reaction of iodobenzene (0.204 g, 1 mmol) and phenyl vinyl
sulfide (0.272 g, 2 mmol) afforded 12; yield: 0.117 g (55%).
This compound was not obtained in pure form, characteristic NMR
signals:
1H NMR (300 MHz, CDCl3): d = 7.45–7.20 (m, 10 H), 6.88 (d,
J = 15.5 Hz, 1 H), 6.72 (d, J = 15.5 Hz, 1 H).
1H NMR (300 MHz, CDCl3): d = 6.82 (d, J = 15.6 Hz, 1 H), 6.45
(d, J = 15.6 Hz, 1 H).
(E)-4-[2-(Phenylsulfinyl)vinyl]acetophenone (13)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and phen-
yl vinyl sulfoxide (0.304 g, 2 mmol) afforded 13; yield: 0.154 g
(57%).
(E)-[2-(Ethylsulfanyl)vinyl]benzene (6)
The reaction of iodobenzene (0.204 g, 1 mmol) and ethyl vinyl sul-
fide (0.176 g, 2 mmol) afforded 6 in 11% (0.018 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.93 (d, J = 8.5 Hz, 2 H), 7.68 (m,
2 H), 7.55–7.48 (m, 5 H), 7.39 (d, J = 15.7 Hz, 1 H), 6.94 (d,
J = 15.7 Hz, 1 H), 2.59 (s, 3 H).
This compound was not obtained in pure form, characteristic NMR
signal:
13C NMR (75 MHz, CDCl3): d = 197.2, 143.4, 138.0, 137.6, 135.7,
134.1, 131.4, 129.6, 128.9, 127.8, 124.8, 26.6.
1H NMR (300 MHz, CDCl3): d = 6.45 (d, J = 15.6 Hz, 1 H).
(E)-4-[2-(Phenylsulfanyl)vinyl]acetophenone (7)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and phen-
yl vinyl sulfide (0.272 g, 2 mmol) afforded 7; yield: 0.114 g (45%).
Anal. Calcd for C16H14O2S: C, 71.08; H, 5.22. Found: C, 71.22; H,
5.04.
(E)-4-[2-(Phenylsulfinyl)vinyl]benzophenone (14)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and phen-
yl vinyl sulfoxide (0.304 g, 2 mmol) afforded 14; yield: 0.199 g
(60%).
1H NMR (300 MHz, CDCl3): d = 7.88 (d, J = 8.2 Hz, 2 H), 7.50–
7.20 (m, 7 H), 7.05 (d, J = 15.5 Hz, 1 H), 6.63 (d, J = 15.5 Hz, 1 H),
2.57 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 197.3, 141.1, 135.6, 133.8, 130.8,
129.3, 128.9, 128.4, 128.1, 127.6, 125.8, 26.5.
1H NMR (300 MHz, CDCl3): d = 7.85–7.46 (m, 14 H), 7.42 (d,
J = 15.7 Hz, 1 H), 6.96 (d, J = 15.7 Hz, 1 H).
Anal. Calcd for C16H14OS: C, 75.55; H, 5.55. Found: C, 75.62; H,
5.68.
13C NMR (75 MHz, CDCl3): d = 195.8, 143.4, 138.3, 137.4, 137.3,
135.5, 134.2, 132.6, 131.4, 130.6, 129.9, 129.6, 128.3, 127.5, 124.8.
(E)-4-[2-(Phenylsulfanyl)vinyl]benzophenone (8)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and phen-
yl vinyl sulfide (0.272 g, 2 mmol) afforded 8; yield: 0.133 g (42%).
Anal. Calcd for C21H16O2S: C, 75.88; H, 4.85. Found: C, 76.02; H,
4.67.
(E)-4-[2-(Phenylsulfinyl)vinyl]benzonitrile (15)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and phenyl
vinyl sulfoxide (0.304 g, 2 mmol) afforded 15; yield: 0.157 g (62%).
1H NMR (300 MHz, CDCl3): d = 7.80–7.70 (m, 4 H), 7.55–7.25 (m,
10 H), 7.06 (d, J = 15.5 Hz, 1 H), 6.66 (d, J = 15.5 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 196.0, 140.6, 137.8, 136.0, 133.8,
132.3, 130.7, 129.9, 129.3, 128.7, 128.3, 128.0, 127.6, 127.3, 125.5.
1H NMR (300 MHz, CDCl3): d = 7.70–7.60 (m, 4 H), 7.58–7.48 (m,
5 H), 7.37 (d, J = 15.7 Hz, 1 H), 6.95 (d, J = 15.7 Hz, 1 H).
Anal. Calcd for C21H16OS: C, 79.71; H, 5.10. Found: C, 79.63; H,
5.24.
13C NMR (75 MHz, CDCl3): d = 143.0, 138.0, 136.9, 132.8, 132.6,
131.6, 129.7, 128.1, 124.7, 118.3, 112.8.
(E)-4-[2-(Phenylsulfanyl)vinyl]benzaldehyde (9)
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and phen-
yl vinyl sulfide (0.272 g, 2 mmol) afforded 9; yield: 0.048 g (20%).
Anal. Calcd for C15H11NOS: C, 71.12; H, 4.38. Found: C, 71.30; H,
4.21.
(E)-1-[2-(Phenylsulfinyl)vinyl]-4-(trifluoromethyl)benzene (16)
The reaction of 1-bromo-4-(trifluoromethyl)benzene (0.225 g,
1 mmol) and phenyl vinyl sulfoxide (0.304 g, 2 mmol) afforded 16;
yield: 0.163 g (55%).
This compound was not obtained in pure form:
1H NMR (300 MHz, CDCl3): d = 9.95 (s, 1 H), 7.79 (d, J = 7.8 Hz,
2 H), 7.50–7.25 (m, 7 H), 7.10 (d, J = 15.5 Hz, 1 H), 6.62 (d,
J = 15.5 Hz, 1 H).
1H NMR (300 MHz, CDCl3): d = 7.70–7.65 (m, 2 H), 7.60 (d,
J = 8.5 Hz, 2 H), 7.57–7.48 (m, 5 H), 7.37 (d, J = 15.7 Hz, 1 H),
6.93 (d, J = 15.7 Hz, 1 H).
(E)-4-[2-(Phenylsulfanyl)vinyl]benzonitrile (10)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and phenyl
vinyl sulfide (0.272 g, 2 mmol) afforded 10: 0.114 g (48%).
13C NMR (75 MHz, CDCl3): d = 143.3, 137.1, 135.7, 133.7, 131.5,
131.3 (d, 2JC–F = 32.3 Hz), 129.6, 127.9, 125.8 (q, 3JC–F = 3.5 Hz),
124.7, 123.7 (q, JC–F = 271.9 Hz).
This compound was not obtained in pure form, characteristic NMR
signals:
Anal. Calcd for C15H11F3OS: C, 60.80; H, 3.74. Found: C, 60.71; H,
3.57.
1H NMR (300 MHz, CDCl3): d = 7.06 (d, J = 15.5 Hz, 1 H), 6.54
(d, J = 15.5 Hz, 1 H).
(E)-[2-(Phenylsulfinyl)vinyl]benzene (17)
The reaction of iodobenzene (0.204 g, 1 mmol) and phenyl vinyl
sulfoxide (0.304 g, 2 mmol) afforded 17; yield: 0.148 g (65%).
(E)-1-Fluoro-4-[2-(phenylsulfanyl)vinyl]benzene (11)
The reaction of 1-bromo-4-fluorobenzene (0.175 g, 1 mmol) and
phenyl vinyl sulfide (0.272 g, 2 mmol) afforded 11; yield: 0.035 g
(15% ).
1H NMR (300 MHz, CDCl3): d = 7.72–7.63 (m, 2 H), 7.55–7.30 (m,
9 H), 6.82 (d, J = 15.7 Hz, 1 H).
This compound was not obtained in pure form, characteristic NMR
signals:
(E)-1-[2-(Phenylsulfinyl)vinyl]naphthalene (18)
The reaction of 1-bromonaphthalene (0.207 g, 1 mmol) and phenyl
vinyl sulfoxide (0.304 g, 2 mmol) afforded 18; yield: 0.189 g (65%).
1H NMR (300 MHz, CDCl3): d = 7.05 (d, J = 15.5 Hz, 1 H), 6.63
(d, J = 15.5 Hz, 1 H).
Synthesis 2006, No. 20, 3495–3505 © Thieme Stuttgart · New York

3502
A. Battace et al.
PAPER
1H NMR (300 MHz, CDCl3): d = 8.19 (d, J = 15.2 Hz, 1 H), 8.18
(d, J = 8.2 Hz, 1 H), 7.87 (d, J = 8.4 Hz, 2 H), 7.73 (d, J = 8.2 Hz,
2 H), 7.63–7.46 (m, 6 H), 7.43 (t, J = 7.5 Hz, 1 H), 6.91 (d, J = 15.2
Hz, 1 H).
(E)-4-[2-(Methylsulfonyl)vinyl]benzonitrile (24)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and methyl
vinyl sulfone (0.212 g, 2 mmol) afforded 24; yield: 0.193 g (93%).
1H NMR (300 MHz, CDCl3): d = 7.72 (d, J = 8.4 Hz, 2 H), 7.64 (d,
J = 15.5 Hz, 1 H), 7.61 (d, J = 8.4 Hz, 2 H), 7.02 (d, J = 15.5 Hz, 1
H), 3.05 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 143.9, 135.7, 133.6, 133.4, 131.2,
131.0, 130.1, 129.5, 129.4, 128.7, 126.9, 126.3, 125.3, 125.1, 124.8,
123.3.
(E)-1-[2-(Methylsulfonyl)vinyl]-4-(trifluoromethyl)benzene
(25)
The reaction of 1-bromo-4-(trifluoromethyl)benzene (0.225 g, 1
mmol) and methyl vinyl sulfone (0.212 g, 2 mmol) afforded 25;
yield: 0.235 g (94%).
Anal. Calcd for C18H14OS: C, 77.66; H, 5.07. Found: C, 77.79; H,
5.28.
(E)-[2-(Methylsulfonyl)vinyl]benzene (19)
The reaction of iodobenzene (0.204 g, 1 mmol) and methyl vinyl
sulfone (0.212 g, 2 mmol) afforded 19; yield: 0.168 g (92%).
1H NMR (300 MHz, CDCl3): d = 7.67 (d, J = 8.3 Hz, 2 H), 7.62 (d,
J = 15.5 Hz, 1 H), 7.61 (d, J = 8.3 Hz, 2 H), 7.01 (d, J = 15.5 Hz, 1
H), 3.03 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.63 (d, J = 15.5 Hz, 1 H), 7.51
(m, 2 H), 7.43 (m, 3 H), 6.91 (d, J = 15.5 Hz, 1 H), 3.02 (s, 3 H).
(E)-1-Fluoro-4-[2-(methylsulfonyl)vinyl]benzene (26)
The reaction of 1-bromo-4-fluorobenzene (0.175 g, 1 mmol) and
methyl vinyl sulfone (0.212 g, 2 mmol) afforded 26; yield: 0.192 g
(96%).
(E)-4-[2-(Methylsulfonyl)vinyl]acetophenone (20)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and meth-
yl vinyl sulfone (0.212 g, 2 mmol) afforded 20; yield: 0.209 g
(93%).
1H NMR (300 MHz, CDCl3): d = 7.59 (d, J = 15.5 Hz, 1 H), 7.51
(dd, J = 8.5, 5.3 Hz, 2 H), 7.12 (t, J = 8.5 Hz, 2 H), 6.84 (d, J = 15.5
Hz, 1 H), 3.03 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.99 (d, J = 8.2 Hz, 2 H), 7.65 (d,
J = 15.5 Hz, 1 H), 7.61 (d, J = 8.2 Hz, 2 H), 7.01 (d, J = 15.5 Hz, 1
H), 3.05 (s, 3 H), 2.62 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 197.0, 142.4, 138.9, 136.2, 129.0,
128.7, 128.6, 43.1, 26.7.
(E)-4-[2-(Methylsulfonyl)vinyl]toluene (27)
The reaction of 4-bromotoluene (0.171 g, 1 mmol) and methyl vinyl
sulfone (0.212 g, 2 mmol) afforded 27; yield: 0.177 g (90%).
Anal. Calcd for C11H12O3S: C, 58.91; H, 5.39. Found: C, 59.07; H,
5.49.
1H NMR (300 MHz, CDCl3): d = 7.58 (d, J = 15.5 Hz, 1 H), 7.39
(d, J = 8.3 Hz, 2 H), 7.21 (d, J = 8.3 Hz, 2 H), 6.85 (d, J = 15.5 Hz,
1 H), 3.01 (s, 3 H), 2.38 (s, 3 H).
(E)-4-[2-(Methylsulfonyl)vinyl]benzophenone (21)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and meth-
yl vinyl sulfone (0.212 g, 2 mmol) afforded 21; yield: 0.263 g
(92%).
(E)-1-tert-Butyl-4-[2-(methylsulfonyl)vinyl]benzene (28)
The reaction of 1-bromo-4-tert-butylbenzene (0.213 g, 1 mmol) and
methyl vinyl sulfone (0.212 g, 2 mmol) afforded 28; yield: 0.219 g
(92%).
1H NMR (300 MHz, CDCl3): d = 7.85 (d, J = 8.2 Hz, 2 H), 7.78 (d,
J = 8.2 Hz, 2 H), 7.69 (d, J = 15.5 Hz, 1 H), 7.63 (d, J = 8.2 Hz, 2
H), 7.61 (t, J = 7.6 Hz, 1 H), 7.49 (t, J = 7.6 Hz, 2 H), 7.02 (d,
J = 15.5 Hz, 1 H), 3.06 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.51 (d, J = 15.5 Hz, 1 H), 7.44
(m, 4 H), 6.86 (d, J = 15.5 Hz, 1 H), 3.01 (s, 3 H), 1.32 (s, 9 H).
13C NMR (75 MHz, CDCl3): d = 195.6, 142.6, 139.7, 137.0, 135.6,
132.9, 130.6, 130.0, 128.5, 128.4, 128.3, 43.2.
13C NMR (75 MHz, CDCl3): d = 155.1, 143.9, 129.3, 128.4, 126.1,
125.1, 43.3, 35.0, 31.1.
Anal. Calcd for C16H14O3S: C, 67.11; H, 4.93. Found: C, 66.91; H,
4.91.
Anal. Calcd for C13H18O2S: C, 65.51; H, 7.61. Found: C, 65.70; H,
7.50.
(E)-4-[2-(Methylsulfonyl)vinyl]benzaldehyde (22)
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and meth-
yl vinyl sulfone (0.212 g, 2 mmol) afforded 22; yield: 0.189 g
(90%).
(E)-4-[2-(Methylsulfonyl)vinyl]anisole (29)
The reaction of 4-bromoanisole (0.187 g, 1 mmol) and methyl vinyl
sulfone (0.212 g, 2 mmol) afforded 29; yield: 0.202 g (95%).
1H NMR (300 MHz, CDCl3): d = 7.56 (d, J = 15.5 Hz, 1 H), 7.46
(d, J = 8.5 Hz, 2 H), 6.93 (d, J = 8.5 Hz, 2 H), 6.74 (d, J = 15.5 Hz,
1 H), 3.84 (s, 3 H), 3.01 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 10.04 (s, 1 H), 7.93 (d, J = 7.9 Hz,
2 H), 7.67 (d, J = 7.9 Hz, 2 H), 7.66 (d, J = 15.5 Hz, 1 H), 7.04 (d,
J = 15.5 Hz, 1 H), 3.05 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 191.1, 142.2, 137.9, 137.5, 130.3,
129.3, 129.0, 43.1.
(E)-3-[2-(Methylsulfonyl)vinyl]acetophenone (30)
The reaction of 3-bromoacetophenone (0.199 g, 1 mmol) and meth-
yl vinyl sulfone (0.212 g, 2 mmol) afforded 30; yield: 0.211 g
(94%).
Anal. Calcd for C10H10O3S: C, 57.13; H, 4.79. Found: C, 57.22; H,
4.51.
1H NMR (300 MHz, CDCl3): d = 8.10 (s, 1 H), 8.01 (d, J = 7.5 Hz,
1 H), 7.69 (d, J = 7.5 Hz, 1 H), 7.66 (d, J = 15.5 Hz, 1 H), 7.54 (t,
J = 7.5 Hz, 1 H), 7.01 (d, J = 15.5 Hz, 1 H), 3.04 (s, 3 H), 2.63 (s,
3 H).
Methyl (E)-4-[2-(Methylsulfonyl)vinyl]benzoate (23)
The reaction of methyl 4-bromobenzoate (0.215 g, 1 mmol) and
methyl vinyl sulfone (0.212 g, 2 mmol) afforded 23; yield: 0.211 g
(88%).
13C NMR (75 MHz, CDCl3): d = 197.0, 142.8, 137.9, 132.8, 132.7,
130.9, 129.6, 128.0, 127.7, 43.2, 26.6.
1H NMR (300 MHz, CDCl3): d = 8.08 (d, J = 7.7 Hz, 2 H), 7.65 (d,
J = 15.5 Hz, 1 H), 7.57 (d, J = 7.7 Hz, 2 H), 6.99 (d, J = 15.5 Hz, 1
H), 3.93 (s, 3 H), 3.04 (s, 3 H).
Anal. Calcd for C11H12O3S: C, 58.91; H, 5.39. Found: C, 58.77; H,
5.27.
Synthesis 2006, No. 20, 3495–3505 © Thieme Stuttgart · New York

PAPER
Heck Vinylations Catalyzed by a Palladium Complex Derived from a Tetraphosphine
3503
(E)-3-[2-(Methylsulfonyl)vinyl]benzaldehyde (31)
The reaction of 3-bromobenzaldehyde (0.185 g, 1 mmol) and meth-
yl vinyl sulfone (0.212 g, 2 mmol) afforded 31; yield: 0.196 g
(93%).
(E)-1,3,5-Trimethyl-2-[2-(methylsulfonyl)vinyl]benzene (36)
The reaction of 1-bromo-2,4,6-trimethylbenzene (0.199 g, 1 mmol)
and methyl vinyl sulfone (0.212 g, 2 mmol) afforded 36; yield:
0.206 g (92%).
1H NMR (300 MHz, CDCl3): d = 10.04 (s, 1 H), 8.02 (s, 1 H), 7.94
(d, J = 7.5 Hz, 1 H), 7.75 (d, J = 7.5 Hz, 1 H), 7.67 (d, J = 15.5 Hz,
1 H), 7.61 (t, J = 7.5 Hz, 1 H), 7.05 (d, J = 15.5 Hz, 1 H), 3.05 (s, 3
H).
1H NMR (300 MHz, CDCl3): d = 7.81 (d, J = 15.5 Hz, 1 H), 6.91
(s, 2 H), 6.59 (d, J = 15.5 Hz, 1 H), 3.03 (s, 3 H), 2.34 (s, 6 H), 2.29
(s, 3 H).
13C NMR (75 MHz, CDCl3): d = 142.5, 140.1, 137.6, 131.0, 129.9,
128.6, 43.7, 31.3, 21.5.
13C NMR (75 MHz, CDCl3): d = 191.2, 142.2, 137.0, 134.0, 133.1,
132.1, 130.0, 128.9, 128.2, 43.1.
Anal. Calcd for C12H16O2S: C, 64.25; H, 7.19. Found: C, 64.10; H,
7.03.
Anal. Calcd for C10H10O3S: C, 57.13; H, 4.79. Found: C, 57.40; H,
4.89.
(E)-9-[2-(Methylsulfonyl)vinyl]anthracene (37)
The reaction of 9-bromoanthracene (0.257 g, 1 mmol) and methyl
vinyl sulfone (0.212 g, 2 mmol) afforded 37; yield: 0.254 g (90%).
(E)-1-[2-(Methylsulfonyl)vinyl]-3,5-bis(trifluoromethyl)ben-
zene (32)
The reaction of 1-bromo-3,5-bis(trifluoromethyl)benzene (0.293 g,
1 mmol) and methyl vinyl sulfone (0.212 g, 2 mmol) afforded 32;
yield: 0.264 g (83%).
1H NMR (300 MHz, CDCl3): d = 8.62 (d, J = 15.5 Hz, 1 H), 8.50
(s, 1 H), 8.16 (d, J = 8.0 Hz, 2 H), 8.03 (d, J = 7.7 Hz, 2 H), 7.55
(m, 4 H), 6.99 (d, J = 15.5 Hz, 1 H), 3.18 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.94 (m, 3 H), 7.69 (d, J = 15.5
Hz, 1 H), 7.11 (d, J = 15.5 Hz, 1 H), 3.07 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 141.1, 134.6, 131.1, 129.4, 129.3,
129.0, 127.0, 125.6, 124.4, 122.6, 43.2.
13C NMR (75 MHz, CDCl3): d = 140.4, 134.3, 132.8 (q, J = 33.8
Hz), 130.4, 128.2 (m), 124.5 (m), 122.7 (q, J = 273.1 Hz), 43.0.
Anal. Calcd for C17H14O2S: C, 72.31; H, 5.00. Found: C, 72.10; H,
4.87.
Anal. Calcd for C11H8F6O2S: C, 41.52; H, 2.53. Found: C, 41.74; H,
2.67.
(E)-1,3,5-Triisopropyl-2-[2-(methylsulfonyl)vinyl]benzene (38)
The reaction of 1-bromo-2,4,6-triisopropylbenzene (0.283 g, 1
mmol) and methyl vinyl sulfone (0.212 g, 2 mmol) afforded 38;
yield: 0.260 g (84%).
(E)-2-[2-(Methylsulfonyl)vinyl]benzonitrile (33)
The reaction of 2-bromobenzonitrile (0.182 g, 1 mmol) and methyl
vinyl sulfone (0.212 g, 2 mmol) afforded 33; yield: 0.182 g (88%).
1H NMR (300 MHz, CDCl3): d = 7.90 (d, J = 15.5 Hz, 1 H), 7.03
(s, 2 H), 6.48 (d, J = 15.5 Hz, 1 H), 3.03 (sept, J = 6.8 Hz, 2 H), 3.02
(s, 3 H), 2.88 (sept, J = 6.8 Hz, 1 H), 1.25 (d, J = 6.8 Hz, 6 H), 1.20
(d, J = 6.8 Hz, 12 H).
1H NMR (300 MHz, CDCl3): d = 7.87 (d, J = 15.5 Hz, 1 H), 7.76
(d, J = 7.3 Hz, 1 H), 7.67 (m, 2 H), 7.57 (m, 1 H), 7.20 (d, J = 15.5
Hz, 1 H), 3.08 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 139.1, 134.8, 134.0, 133.2, 131.4,
131.1, 128.5, 116.8, 112.7, 43.1.
13C NMR (75 MHz, CDCl3): d = 149.9, 146.3, 143.9, 132.0, 127.4,
121.1, 43.0, 34.3, 30.3, 23.9, 23.8.
Anal. Calcd for C10H9NO2S: C, 57.95; H, 4.38. Found: C, 57.71; H,
4.55.
Anal. Calcd for C18H28O2S: C, 70.08; H, 9.15. Found: C, 70.01; H,
9.32.
(E)-1-[2-(Methylsulfonyl)vinyl]naphthalene (34)
The reaction of 1-bromonaphthalene (0.207 g, 1 mmol) and methyl
vinyl sulfone (0.212 g, 2 mmol) afforded 34; yield: 0.218 g (94%).
(E)-3-[2-(Methylsulfonyl)vinyl]pyridine (39)
The reaction of 3-bromopyridine (0.158 g, 1 mmol) and methyl vi-
nyl sulfone (0.212 g, 2 mmol) afforded 39; yield: 0.165 g (90%).
1H NMR (300 MHz, CDCl3): d = 8.45 (d, J = 15.1 Hz, 1 H), 8.14
(d, J = 8.3 Hz, 1 H), 7.94 (d, J = 8.1 Hz, 1 H), 7.90 (d, J = 8.1 Hz,
1 H), 7.73 (d, J = 8.1 Hz, 1 H), 7.65–7.45 (m, 3 H), 7.02 (d, J = 15.1
Hz, 1 H), 3.09 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 8.72 (m, 2 H), 7.81 (d, J = 5.8 Hz,
1 H), 7.56 (d, J = 15.4 Hz, 1 H), 7.35 (m, 1 H), 7.02 (d, J = 15.4 Hz,
1 H), 3.00 (s, 3 H).
(E)-4-[2-(Methylsulfonyl)vinyl]pyridine (40)
The reaction of 4-bromopyridine (0.158 g, 1 mmol) and methyl vi-
nyl sulfone (0.212 g, 2 mmol) afforded 40; yield: 0.167 g (91%).
13C NMR (75 MHz, CDCl3): d = 141.2, 133.7, 131.7, 131.3, 129.2,
128.9, 128.5, 127.4, 126.6, 125.7, 125.3, 123.0, 43.3.
Anal. Calcd for C13H12O2S: C, 67.21; H, 5.21. Found: C, 67.41; H,
5.30.
1H NMR (300 MHz, CDCl3): d = 8.67 (d, J = 6.0 Hz, 2 H), 7.53 (d,
J = 15.4 Hz, 1 H), 7.35 (d, J = 6.0 Hz, 2 H), 7.11 (d, J = 15.4 Hz, 1
H), 3.03 (s, 3 H).
(E)-2-[2-(Methylsulfonyl)vinyl]anisole (35)
The reaction of 2-bromoanisole (0.187 g, 1 mmol) and methyl vinyl
sulfone (0.212 g, 2 mmol) afforded 35; yield: 0.170 g (80%).
(E)-3-[2-(Methylsulfonyl)vinyl]quinoline (41)
The reaction of 3-bromoquinoline (0.208 g, 1 mmol) and methyl vi-
nyl sulfone (0.212 g, 2 mmol) afforded 41; yield: 0.212 g (91%).
1H NMR (300 MHz, CDCl3): d = 7.79 (d, J = 15.1 Hz, 1 H), 7.45–
7.37 (m, 2 H), 7.14 (d, J = 15.1 Hz, 1 H), 6.99 (t, J = 7.7 Hz, 1 H),
6.94 (d, J = 7.7 Hz, 1 H), 3.91 (s, 3 H), 3.01 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 9.06 (d, J = 2.2 Hz, 1 H), 8.26 (d,
J = 2.2 Hz, 1 H), 8.13 (d, J = 8.5 Hz, 1 H), 7.87 (d, J = 8.5 Hz, 1 H),
7.79 (t, J = 7.8 Hz, 1 H), 7.78 (d, J = 15.6 Hz, 1 H), 7.59 (t, J = 7.8
Hz, 1 H), 7.15 (d, J = 15.6 Hz, 1 H), 3.00 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 158.9, 139.9, 132.6, 131.0, 128.8,
127.0, 120.9, 111.3, 55.5, 43.4.
13C NMR (75 MHz, CDCl3): d = 149.0, 148.8, 140.7, 136.7, 131.4,
129.5, 128.5, 127.9, 127.8, 127.4, 125.1, 43.2.
Anal. Calcd for C10H12O3S: C, 56.58; H, 5.70. Found: C, 56.40; H,
5.87.
Anal. Calcd for C12H11NO2S: C, 61.78; H, 4.75. Found: C, 61.52; H,
4.81.
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3504
A. Battace et al.
PAPER
(E)-1-[2-(Phenylsulfonyl)vinyl]-4-(trifluoromethyl)benzene
(48)
The reaction of 1-bromo-4-(trifluoromethyl)benzene (0.225 g,
1 mmol) and phenyl vinyl sulfone (0.336 g, 2 mmol) afforded 48;
yield: 0.265 g (85%).
(E)-4-[2-(Methylsulfonyl)vinyl]isoquinoline (42)
The reaction of 4-bromoisoquinoline (0.208 g, 1 mmol) and methyl
vinyl sulfone (0.212 g, 2 mmol) afforded 42; yield: 0.208 g (89%).
1H NMR (300 MHz, CDCl3): d = 9.29 (s, 1 H), 8.73 (s, 1 H), 8.31
(d, J = 15.5 Hz, 1 H), 8.11 (d, J = 8.5 Hz, 1 H), 8.05 (d, J = 8.5 Hz,
1 H), 7.84 (t, J = 7.6 Hz, 1 H), 7.73 (t, J = 7.6 Hz, 1 H), 7.11 (d,
J = 15.5 Hz, 1 H), 3.11 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.95 (d, J = 8.2 Hz, 2 H), 7.70 (d,
J = 15.5 Hz, 1 H), 7.68–7.52 (m, 7 H), 6.96 (d, J = 15.5 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 155.1, 142.1, 138.3, 133.5, 131.8,
129.9, 128.5, 128.2, 128.1, 123.4, 122.2, 43.1.
(E)-1-Fluoro-4-[2-(phenylsulfonyl)vinyl]benzene (49)
The reaction of 1-bromo-4-fluorobenzene (0.175 g, 1 mmol) and
phenyl vinyl sulfone (0.336 g, 2 mmol) afforded 49; yield: 0.244 g
(93%).
Anal. Calcd for C12H11NO2S: C, 61.78; H, 4.75. Found: C, 61.57; H,
4.79.
1H NMR (300 MHz, CDCl3): d = 7.93 (d, J = 8.0 Hz, 2 H), 7.63 (d,
J = 15.5 Hz, 1 H), 7.58–7.50 (m, 3 H), 7.46 (dd, J = 5.5, 8.3 Hz, 2
H), 7.07 (t, J = 8.3 Hz, 2 H), 6.77 (d, J = 15.5 Hz, 1 H).
(E)-2-[2-(Methylsulfonyl)vinyl]thiophene (43)
The reaction of 2-bromothiophene (0.163 g, 1 mmol) and methyl vi-
nyl sulfone (0.212 g, 2 mmol) afforded 43; yield: 0.164 g (87%).
1H NMR (300 MHz, CDCl3): d = 7.55 (d, J = 15.4 Hz, 1 H), 7.34
(d, J = 5.1 Hz, 1 H), 7.19 (d, J = 3.6 Hz, 1 H), 6.94 (dd, J = 5.1, 3.6
Hz, 1 H), 6.59 (d, J = 15.4 Hz, 1 H), 2.88 (s, 3 H).
(E)-4-[2-(Phenylsulfonyl)vinyl]toluene (50)
The reaction of 4-bromotoluene (0.171 g, 1 mmol) and phenyl vinyl
sulfone (0.336 g, 2 mmol) afforded 50; yield: 0.232 g (90%).
1H NMR (300 MHz, CDCl3): d = 7.93 (d, J = 8.0 Hz, 2 H), 7.60 (d,
J = 15.5 Hz, 1 H), 7.59–7.49 (m, 3 H), 7.39 (d, J = 7.9 Hz, 2 H),
7.18 (d, J = 7.9 Hz, 2 H), 6.79 (d, J = 15.5 Hz, 1 H), 2.36 (s, 3 H).
(E)-4-[2-(Phenylsulfonyl)vinyl]acetophenone (44)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and phen-
yl vinyl sulfone (0.336 g, 2 mmol) afforded 44; yield: 0.263 g
(92%).
(E)-4-[2-(Phenylsulfonyl)vinyl]anisole (51)
The reaction of 4-bromoanisole (0.187 g, 1 mmol) and phenyl vinyl
sulfone (0.336 g, 2 mmol) afforded 51; yield: 0.195 g (71%).
1H NMR (300 MHz, CDCl3): d = 7.95 (d, J = 8.2 Hz, 4 H), 7.69 (d,
J = 15.5 Hz, 1 H), 7.65–7.50 (m, 5 H), 6.95 (d, J = 15.5 Hz, 1 H),
2.60 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.93 (d, J = 8.0 Hz, 2 H), 7.62 (d,
J = 15.5 Hz, 1 H), 7.58–7.46 (m, 3 H), 7.42 (d, J = 8.0 Hz, 2 H),
6.89 (d, J = 8.0 Hz, 2 H), 6.70 (d, J = 15.5 Hz, 1 H), 3.82 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 197.1, 140.7, 140.2, 138.7, 136.6,
133.6, 129.8, 129.4, 128.9, 128.7, 127.8, 26.7.
(E)-4-[2-(Phenylsulfonyl)vinyl]benzophenone (45)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and phe-
nyl vinyl sulfone (0.336 g, 2 mmol) afforded 45; yield: 0.306 g
(88%).
(E)-1-[2-(Phenylsulfonyl)vinyl]naphthalene (52)
The reaction of 1-bromonaphthalene (0.207 g, 1 mmol) and phenyl
vinyl sulfone (0.336 g, 2 mmol) afforded 52; yield: 0.191 g (65%).
1H NMR (300 MHz, CDCl3): d = 8.51 (d, J = 15.2 Hz, 1 H), 8.14
(d, J = 8.2 Hz, 1 H), 7.99 (d, J = 8.4 Hz, 2 H), 7.90 (d, J = 8.2 Hz,
1 H), 7.86 (d, J = 8.2 Hz, 1 H), 7.65–7.48 (m, 6 H), 7.43 (t, J = 7.5
Hz, 1 H), 6.95 (d, J = 15.2 Hz, 1 H).
1H NMR (300 MHz, CDCl3): d = 7.97 (d, J = 8.2 Hz, 2 H), 7.85–
7.43 (m, 13 H), 6.97 (d, J = 15.5 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 195.6, 140.9, 140.3, 139.5, 137.0,
135.9, 133.6, 132.8, 130.6, 129.9, 129.7, 129.4, 128.4, 128.3, 127.8.
(E)-2-[2-(Phenylsulfonyl)vinyl]toluene (53)
The reaction of 2-bromotoluene (0.171 g, 1 mmol) and phenyl vinyl
sulfone (0.336 g, 2 mmol) afforded 53; yield: 0.129 g (50%).
Anal. Calcd for C21H16O3S: C, 72.39; H, 4.63. Found: C, 72.51; H,
4.80.
1H NMR (300 MHz, CDCl3): d = 7.97 (d, J = 15.2 Hz, 1 H), 7.95
(d, J = 8.2 Hz, 2 H), 7.62–7.50 (m, 3 H), 7.42 (d, J = 8.2 Hz, 1 H),
7.29 (t, J = 8.0 Hz, 1 H), 7.25–7.12 (m, 2 H), 6.77 (d, J = 15.2 Hz,
1 H), 2.45 (s, 3 H).
(E)-4-[2-(Phenylsulfonyl)vinyl]benzaldehyde (46)
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and phen-
yl vinyl sulfone (0.336 g, 2 mmol) afforded 46; yield: 0.240 g
(88%).
1H NMR (300 MHz, CDCl3): d = 10.02 (s, 1 H), 7.96 (d, J = 8.2 Hz,
2 H), 7.90 (d, J = 8.2 Hz, 2 H), 7.70 (d, J = 15.5 Hz, 1 H), 7.65–7.50
(m, 5 H), 6.98 (d, J = 15.5 Hz, 1 H).
Phenyl (E)-2-(4-Cyanophenyl)ethenesulfonate (54)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and phenyl
vinylsulfonate (0.368 g, 2 mmol) afforded 54; yield: 0.251 g (88%).
13C NMR (75 MHz, CDCl3): d = 191.1, 140.5, 140.1, 137.9, 137.7,
133.7, 130.5, 130.2, 129.4, 129.0, 127.8.
1H NMR (300 MHz, CDCl3): d = 7.80–7.19 (m, 10 H), 6.97 (d,
J = 15.2 Hz, 1 H).
Anal. Calcd for C15H12O3S: C, 66.16; H, 4.44. Found: C, 66.00; H,
4.37.
13C NMR (75 MHz, CDCl3): d = 143.4, 132.9, 132.8, 130.0, 128.9,
127.9, 127.5, 124.4, 122.3, 117.8, 114.9.
Anal. Calcd for C15H11NO3S: C, 63.14; H, 3.89. Found: C, 62.95; H,
4.07.
(E)-4-[2-(Phenylsulfonyl)vinyl]benzonitrile (47)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and phenyl
vinyl sulfone (0.336 g, 2 mmol) afforded 47; yield: 0.121 g (45%).
Phenyl (E)-2-(4-Methoxyphenyl)ethenesulfonate (55)
The reaction of 4-bromoanisole (0.187 g, 1 mmol) and phenyl vi-
nylsulfonate (0.368 g, 2 mmol) afforded 55; yield: 0.250 g (86%).
1H NMR (300 MHz, CDCl3): d = 7.94 (d, J = 8.2 Hz, 2 H), 7.70–
7.50 (m, 8 H), 6.95 (d, J = 15.5 Hz, 1 H).
1H NMR (300 MHz, CDCl3): d = 7.50–7.20 (m, 8 H), 6.91 (d,
J = 8.2 Hz, 2 H), 6.69 (d, J = 15.2 Hz, 1 H), 3.84 (s, 3 H).
Synthesis 2006, No. 20, 3495–3505 © Thieme Stuttgart · New York

PAPER
Heck Vinylations Catalyzed by a Palladium Complex Derived from a Tetraphosphine
3505
13C NMR (75 MHz, CDCl3): d = 162.5, 149.6, 145.9, 130.5, 129.8,
127.1, 124.3, 122.5, 117.6, 114.7, 55.5.
Nakahara, H.; Shimaya, J.; Tsukamoto, S.-I.; Tanaka, A.;
Yanagisawa, I. Bioorg. Med. Chem. 2001, 9, 2955.
(c) Harada, H.; Kazami, J.-I.; Watanuki, S.; Tsuzuki, R.;
Sudoh, K.; Fujimori, A.; Tokunaga, T.; Tanaka, A.;
Tsukamoto, S.-I.; Yanagisawa, I. Chem. Pharm. Bull. 2001,
49, 1593. (d) Hirayama, F.; Koshio, H.; Ishihara, T.;
Watanuki, S.; Hachiya, S.; Kaizawa, H.; Kuramochi, T.;
Katayama, N.; Kurihara, H.; Taniuchi, Y.; Sato, K.; Sakai-
Moritani, Y.; Kaku, S.; Kawasaki, T.; Matsumoto, Y.;
Sakamoto, S.; Tsukamoto, S.-I. Bioorg. Med. Chem. 2002,
10, 2597.
Anal. Calcd for C15H14O4S: C, 62.05; H, 4.86. Found: C, 61.87; H,
4.71.
Phenyl (E)-2-(1-Naphthyl)ethenesulfonate (56)
The reaction of 1-bromonaphthalene (0.207 g, 1 mmol) and phenyl
vinyl sulfonate (0.368 g, 2 mmol) afforded 56; yield: 0.264 g (85%).
1H NMR (300 MHz, CDCl3): d = 8.30 (d, J = 15.2 Hz, 1 H), 7.95
(d, J = 8.1 Hz, 1 H), 7.90–7.84 (m, 2 H), 7.67 (d, J = 8.1 Hz, 1 H),
7.57–7.47 (m, 3 H), 7.42–7.23 (m, 5 H), 6.94 (d, J = 15.2 Hz, 1 H).
(9) (a) Dickinson, R. P.; Dack, K. N.; Long, C. J.; Steele, J. J.
Med. Chem. 1997, 40, 3442. (b) Orita, A.; Katakami, M.;
Yasui, Y.; Kurihara, A.; Otera, J. Green Chem. 2001, 3, 13.
(10) Berteina, S.; Wendeborn, S.; Brill, W. K.-D.; De
Mesmaeker, A. Synlett 1998, 676.
(11) Uozumi, Y.; Kimura, T. Synlett 2002, 2045.
(12) Zeng, B.-B.; King, S. B. Synthesis 2002, 2335.
(13) Laurenti, D.; Feuerstein, M.; Pèpe, G.; Doucet, H.; Santelli,
M. J. Org. Chem. 2001, 66, 1633.
(14) Feuerstein, M.; Laurenti, D.; Bougeant, C.; Doucet, H.;
Santelli, M. Chem. Commun. 2001, 325.
(15) Feuerstein, M.; Berthiol, F.; Doucet, H.; Santelli, M. Org.
Biomol. Chem. 2003, 1, 2235.
13C NMR (75 MHz, CDCl3): d = 149.6, 143.8, 133.6, 131.9, 131.1,
129.9, 129.0, 128.8, 127.4, 127.3, 126.6, 125.8, 125.3, 123.0, 122.9,
122.5.
Anal. Calcd for C18H14O3S: C, 69.66; H, 4.55. Found: C, 69.50; H,
4.82.
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Synthesis 2006, No. 20, 3495–3505 © Thieme Stuttgart · New York