Stereo-recognizing transformation of (E)-alkenyl halides into sulfides catalyzed by nickel(0) triethyl phosphite complex

Article abstract of DOI:10.1016/j.tet.2006.08.001

(E)-Alkenyl halides were transformed into (E)-alkenyl sulfides by the nickel(0) triethyl phosphite complex-catalyzed reaction with thiols, whereas (Z)-alkenyl halides gave alkynes under the same reaction conditions. Aryl halides were also transformed into aryl sulfides using the same reagent system.

Full text of DOI:10.1016/j.tet.2006.08.001

Tetrahedron 62 (2006) 9981–9987
Stereo-recognizing transformation of (E)-alkenyl halides into
sulfides catalyzed by nickel(0) triethyl phosphite complex
*
Yasutaka Yatsumonji, Orie Okada, Akira Tsubouchi and Takeshi Takeda
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology,
Koganei, Tokyo 184-8588, Japan
Received 12 July 2006; revised 28 July 2006; accepted 1 August 2006
Available online 21 August 2006
Abstract—(E)-Alkenyl halides were transformed into (E)-alkenyl sulfides by the nickel(0) triethyl phosphite complex-catalyzed reaction
with thiols, whereas (Z)-alkenyl halides gave alkynes under the same reaction conditions. Aryl halides were also transformed into aryl sulfides
using the same reagent system.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
for the stereoselective transformation of alkenyl halides
into sulfides using a less expensive and air-stable catalyst
and found that nickel(0) triethyl phosphite complex 111
was extremely effective for the conversion. The nickel cata-
lyst 1 is easily prepared by the treatment of nickel(II) chlo-
ride with triethyl phosphite and is stable in air.
Alkenyl sulfides are useful synthetic intermediates and are
employed as precursors for acyl anion equivalents,1 equiva-
lents of enolates,2 Michael acceptors,3 components of
[2+2] cycloadditions,4 and synthetic intermediates for cer-
tain cyclic compounds.5 Among various methods for their
preparations, the transition metal-catalyzed transformation
of alkenyl halides or triflates into alkenyl sulfides has
attracted much attention in recent years. A variety of palla-
dium(0) complexes have been found to serve as effective
catalysts.6 Transformation of alkenyl halides into sulfides us-
ing a stoichiometric7 or a catalytic8 amount of copper(I) com-
plexes has also been reported. Alkenyl sulfides are obtained
by the s-aryl-Ni[PPh3]2Cl-catalyzed reaction of alkenyl ha-
lides with thiols under phase transfer conditions.6b Bis(bipyr-
idine)nickel(II) bromide also catalyzes the transformation
though rather drastic conditions are indispensable.9
2. Results and discussion
The treatment of b-bromostyrene 2a (E/Z¼85:15–90:10)
with benzenethiol 4a (1.2 equiv) at 120 ꢀC in the presence
of 1 (5 mol %) and triethylamine (2 equiv) in DMF produced
b-(phenylthio)styrene 3a in 90% yield (Table 1, entry 1).
The decrease in the yield of 3a was observed when the reac-
tion was carried out at lower temperature (50 ꢀC) (entry 2).
The quantitative formation of 3a was achieved by the reac-
tion using N,N-diethylaniline (2.0 equiv) as a base at 70 ꢀC
(entry 3). The alkenyl sulfide 3a was obtained in satisfactory
yield using 1.5 equiv of N,N-diethylaniline even at 50 ꢀC
(entry 4). On the contrary, the reaction of 2a with cyclo-
hexanethiol 4b under the same reaction conditions gave
no alkenyl sulfide. To increase the nucleophilicity of the
alkanethiol 4b, sodium hydride was used as a base, and the
alkenyl sulfide 3b was obtained in 44% yield along with
40% recovery of the starting material (entry 6). Lengthening
of reaction time gave a similar result, but the starting mate-
rial was completely consumed in a short period of time by
the use of THF as a co-solvent to produce 3b in good yield
(entry 7) (Scheme 1).
In connection with our study on the titanocene(II)-promoted
reaction of alkenyl sulfones with unsaturated compounds,10
we required a practical method for the stereoselective prep-
aration of disubstituted alkenyl sulfides from alkenyl ha-
lides. Despite the above extensive studies, a little has been
known about the stereochemistry of the transformation.8
The foregoing reactions catalyzed by transition metals re-
quire rather high reaction temperature and long reaction
time. The catalysts used in these reactions are either expen-
sive or difficult to be handled in an uncontrolled environ-
ment. Then we explored an alternative practical method
The alkenyl sulfides 3 obtained by the reaction of b-bromo-
styrene 2a were the mixtures of stereoisomers with predom-
inance of E-configuration. We considered the possibility that
Keywords: Cross coupling; Nickel(0) complexes; Thiols; Sulfides.
* Corresponding author. Tel./fax: +81 42 388 7034; e-mail: takeda-t@cc.
tuat.ac.jp
0040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.08.001

9982
Y. Yatsumonji et al. / Tetrahedron 62 (2006) 9981–9987
Table 1. Reaction of b-bromostyrene 2aa with thiols 4
Entry
1
Thiol 4
Base (equiv)
Et3N (2.0)
Solvent
DMF
Temp (ꢀC)
Time (h)
23
Product (yield/%,b
ratio of stereoisomers)
S
SH
120
4a
3a (90, 93:7)
2
3
4
4a
4a
4a
Et3N (2.0)
PhNEt2 (2.0)
PhNEt2 (1.5)
DMF
DMF
DMF
50
70
50
23
23
24
3a (53, 99:1)
3a (98, 89:11)
3a (88, 89:11)
O
S
5c
4a
PhNEt2 (1.5)
DMF
50
24
5a (93, 100:0)
S
SH
6
7
8
NaH (1.5)
NaH (1.5)
NaH (1.5)
DMF
50
50
50
24
3b (44, 88:12)
4b
4b
DMF/THF
DMF/THF
2.5
2.5
3b (93, 88:12)
S
SH
4c
3c (91, 91:9)
O O
S
9c
4c
NaH (1.5)
NaH (1.5)
NaH (1.5)
NaH (1.5)
DMF/THF
DMF/THF
DMF/THF
DMF/THF
50
50
50
50
2.5
2.5
8
6 (78, 100:0)
S
10
11
SH
4d
3d (95, 90:10)
SH
S
4e
3e (90, 90:10)
S
Cl
SH
12
4
Cl
4f
3f (85, 87:13)
a
E/Z¼85:15–90:10.
b
c
Isolated yield.
The alkenyl sulfide 3 was oxidized with MCPBA in the same vessel without any isolation or purification.
SR3
R3SH 4, Ni[P(OEt)3]4 1
X
undeniable that (Z)-b-bromostyrene 2a isomerizes to the
E-isomer under the reaction conditions; such isomerization
explains the excess formation of E-isomers over theoretical
amount estimated by the ratio of stereoisomers of the start-
ing material 2a.
R1
R1
R2
Base
2
R2
3
Scheme 1. Formation of alkenyl sulfides by the reaction of alkenyl halides
with thiols.
the concomitant formation of Z-alkenyl sulfides was due to
the photoisomerization of the E-isomers during and after iso-
lation, since such isomerization has been known.12 Then the
reactions of 2a with 4a and 4c were performed in the dark,
and a dichloromethane solution of m-chloroperbenzoic
acid (MCPBA) (10 equiv) was added to the mixtures to
oxidize the resulting alkenyl sulfides 3a and 3c. The sulfox-
ide 5a formed from the reaction with 4a and the sulfone 5b
formed from that with 4c were single isomers with E-config-
uration (entries 5 and 9).13 These facts indicate that the reac-
tion is stereoselective. If the reaction is stereospecific, it is
The reactions of (E)-1-alkenyl halides 2 and thiols 4 also
gave (E)-alkenyl sulfides 3 in high yields (Table 2). Al-
though the reaction of 2a with 4a gave the alkenyl sulfide
3g as a mixture of stereoisomers, the corresponding sulfox-
ide 5b was obtained as a single stereoisomer by the reaction
in the dark and subsequent oxidation. What is striking is that
the reaction of (Z)-2c with 2-methyl-2-propanethiol 4d gave
no alkenyl sulfide but the alkyne 7a was selectively produced
(entry 6). The elimination also took place in the absence of
the thiol 4d. The result marks a sharp contrast with the con-
ventional transition metal-catalyzed transformations.6a,8

Y. Yatsumonji et al. / Tetrahedron 62 (2006) 9981–9987
Table 2. Reaction of 1-alkenyl halides 2 with thiols 4a
9983
Entry
1
Alkenyl halide 2
Thiol 4
Base (equiv)
PhNEt2 (1.5)
Solvent
DMF
Time (h)
24
Product (yield/%,b ratio of stereoisomers)
I
S
Hex
Hex
4a
3g (90, 52:48)
2b (E:Z = 100:0)
O
S
2c
2b
4a
PhNEt2 (1.5)
DMF
24
5b (86, 100:0)
Hex
S
3
4
2b
2b
4d
4e
NaH (1.5)
NaH (1.5)
DMF/THF
DMF/THF
3
1
3h (91, 100:0)
3i (93, 100:0)
Hex
S
Hex
Hex
S
5
6
2b
4f
NaH (1.5)
NaH (1.5)
DMF/THF
DMF/THF
4
4
3j (89, 82:18)
7a (70, 81d)
Cl
Ph
Ph
Ph
Br
4d
Ph
2c (E:Z = 0:100)
I
S
Pr
Pr
7
8
9
4a
4d
4d
PhNEt2 (1.5)
NaH (1.5)
NaH (1.5)
DMF
26
3
3k (85, 87:13)
3l (98, 100:0)
3m (91, 100:0)
Pr
Pr
2d (E:Z = 100:0)
S
Pr
2d
DMF/THF
DMF/THF
Pr
I
S
Ph(CH2)3
Ph(CH2)3
Ph(CH2)3
2.5
Ph(CH2)3
2e (E:Z = 100:0)
Ph
Ph
Ph
10
11
4d
NaH (1.5)
DMF/THF
1
7b (51)e
Ph
I
2e (E:Z = 12:88)
I
S
Hex
Hex
Me3Si
4a
4f
PhNEt2 (1.5)
PhNEt2 (1.5)
DMF
DMF
24
26
3n (87, 100:0)
3o (86, 100:0)
Me3Si
2f (E:Z = 100:0)
S
Hex
Me3Si
12
2f
Cl
a
All reactions were carried out at 50 ꢀC.
Isolated yield.
The alkenyl sulfide 3 was oxidized with MCPBA in the same vessel without any isolation or purification.
In the absence of 4d.
The corresponding alkenyl sulfide 3m was formed in 7% yield as a single isomer. 1,8-Diphenyl-4-octene was also obtained (9%) and (Z)-2e was recovered
b
c
d
e
(11%).
Similar to the reactions of 1-alkenyl halides, the reaction
mode of highly substituted alkenyl halides was also depen-
dent on its configuration; the treatment of E-2e with 4d in
the presence of 1 produced the E-alkenyl sulfide 3m selec-
tively whereas a similar treatment of Z-2e gave the internal
alkyne 7b (see entries 9 and 10). The loss of stereoselectiv-
ity observed in the reaction of 2d with 4a (entry 7) would be
due to the photoisomerization since the alkenyl sulfide 3k
(E/Z¼83:17) was readily transformed into a one-to-one
mixture of the stereoisomers on standing under fluorescent
light.
A plausible pathway for the nickel(II) 1-promoted reaction of
(E)-alkenyl halides 2 with thiols is illustrated in Scheme 2.
Ligand exchange of the vinylnickel species 8, generated by
the oxidative addition of the halide 2 to 1, with the thiolate
anion and subsequent reductive elimination afford alkenyl
sulfides 3. It is suggested that the b-hydride elimination of or-
ganonickel species is more difficult than that of organopalla-
dium compounds.14 Therefore, the observed preferential
formation of alkynes 7 in the reaction of (Z)-alkenyl halides
2 with thiols would be attributable to the ‘E2 elimination’
shown in Scheme 3 rather than the b-hydride elimination.

9984
Y. Yatsumonji et al. / Tetrahedron 62 (2006) 9981–9987
Table 3. Formation of aryl sulfides 10a
Since the elimination proceeds in an anti-fashion, the substi-
tution is more favorable to the (E)-alkenyl halides than the E2
elimination.
Entry
1
Aryl halide 9
Thiol 4
Time (h)
Aryl sulfide 10
(yield/%)
S
R3S
Cl
Ni(II)X
R1
4b
4
R2
8
9a
10a (-)
X
R1
Br
X
R2
E-2
2
4b
4
10a (78)
9b
Ni(II)SR3
R1
Ni(0) 1
S
R2
I
3b
4c
4a
4b
24
4
10b (90)
10a (90)
9c
SR3
R1
9c
R2
3
S
5
6
9c
4e
4f
8
4
Scheme 2. A plausible mechanism for the formation of alkenyl sulfides from
(E)-alkenyl halides.
10c (91)
S
R1
R1
9c
Ni(0) 1
X
Ni(II) — X
Cl
H
H
10d (88)
R2
R2
Z-2
Base
R2
Br
S
R1
+
1
- Base: HX
7
4c
4
7
10e (81)
9d
Scheme 3. A plausible mechanism for the formation of alkynes from
(Z)-alkenyl halides.
a
All reactions were carried out in DMF/THF at reflux and 1.5 equiv of NaH
was used as a base, unless otherwise noted.
Carried out in DMF at 70 ꢀC using 1.5 equiv of PhNEt2 as a base.
Performed on a 10 mmol scale.
b
c
The formation of p-chlorophenyl sulfides 3f, 3j, and 3o indi-
cates that aryl chlorides are inactive toward the nickel(0)–
thiol system. In fact, the reaction of chlorobenzene 9a with
cyclohexanethiol 4b gave no sulfide and the starting material
was recovered quantitatively. On the contrary, bromobenz-
ene 9b and iodobenzene 9c do react with thiols 4 to produce
aryl sulfides 10 under similar conditions (Scheme 3, Table 3).
The synthetic utility of the present method was demonstrated
by the gram-scale reaction of 9c with 4b (entry 4). The yield
of the sulfide 10a was comparable to the other reactions,
which were performed on a 0.3 mmol scale (Scheme 4).
catalysts for this transformation. The reactions catalyzed
by these nickel complexes, however, suffer from high reac-
tion temperature or long reaction time. The results described
here indicate that nickel(0) triethyl phosphite complex 1 is
a good alternative to the above catalysts.
3. Conclusion
X
SR
RSH 4, Ni[P(OEt)3]4
1
We have developed a practical method for the transformation
of (E)-alkenyl halides into the corresponding (E)-alkenyl sul-
fides using the inexpensive and air-stable nickel(0) catalyst.
In addition, aryl halides are transformed into aryl sulfides
by the same procedure. These reactions proceed under mild
conditions and afford the sulfides in good to high yields. Fur-
ther study on the nickel(0) triethyl phosphite complex-cata-
lyzed CeX bond scission is currently in progress.
Base
9
10
Scheme 4. Formation of aryl sulfides by the reaction of aryl halides with
thiols.
Since aryl sulfides and sulfones are important compounds in
pharmaceutical industry, transition metal-catalyzed coupling
reactions of aryl halides and triflates with thiols have been
extensively studied and a variety of palladium complexes
are employed as a catalyst for the transformation.6b,d,e,g,15
Both stoichiometric16 and catalytic17 amounts of copper(I)
species are also employed. Recently cesium hydroxide
monohydrate-promoted coupling of aryl halides with
thiols was reported.18 Nickel compounds, such as s-aryl-
Ni[PPh3]2Cl,6b o-phenylene-bis[diphenylphosphino]nickel(II)
bromide complex,19 and the nickel(0) species generated
from a nickel(II) bromide-1,10-bis(diphenylphosphino)ferro-
cene–zinc powder system,20 have also been investigated as
4. Experimental
4.1. General
DMF was distilled from calcium hydride under reduced
pressure. THF was distilled from sodium and benzophenone.
Preparative thin-layer chromatography (PTLC) was carried
out using Wakogel B-5F. Tetrakis(triethyl phosphite)-
nickel(0) was prepared according to the literature proce-
dure.11 1H (300 MHz) and 13C (75 MHz) NMR spectra

Y. Yatsumonji et al. / Tetrahedron 62 (2006) 9981–9987
9985
were recorded in CDCl3 on a JEOL AL300. Chemical shifts
(d) were quoted in parts per million from tetramethylsilane
(m, 5H); 13C NMR: 14.5, 15.4, 26.5, 124.8, 125.4, 126.5,
126.7, 126.8, 127.1, 128.2, 128.5, 128.6, 137.1.
1
for H and CDCl3 for 13C NMR spectroscopies. IR spectra
were measured on a JASCO FTIR 460 plus and absorptions
were reported in cmꢁ1. Elemental analyses were performed
on a Perkin–Elmer 2400II analyzer.
4.2.4. 1-Phenyl-2-(tert-butylthio)ethene (3d)8 (E/Z¼
90:10). IR (neat): 3023, 2961, 2924, 2898, 1597, 1457,
1445, 1365, 1162, 944, 740, 691; H NMR: 1.41 (s, 8.1H),
1
1.43 (s, 0.9H), 5.43 (d, J¼11.2 Hz, 0.10H), 5.49 (d,
J¼11.5 Hz, 0.10H), 6.71 (d, J¼15.3 Hz, 0.90H), 6.88 (d,
J¼15.3 Hz, 0.90H), 7.17–7.52 (m, 5H); 13C NMR (E-iso-
mer): 31.0, 44.3, 122.0, 125.8, 127.2, 128.6, 132.0, 137.0.
4.2. Transformation of alkenyl and aryl halides into
sulfides
Typical procedure using benzenethiol: tetrakis(triethyl phos-
phite)nickel(0) (11 mg, 0.015 mmol) was placed in a flask
with DMF (0.3 mL) under argon. A DMF (0.6 mL) solution
of b-bromostyrene (2a) (55 mg, 0.3 mmol), a DMF (0.6 mL)
solution of N,N-diethylaniline (67 mg, 0.45 mmol), and
benzenethiol (4a) (0.94 M in DMF, 0.34 mL, 0.36 mmol)
were successively added to the flask at room temperature.
The mixture was heated to 50 ꢀC and stirred for 24 h. The
reaction was quenched by the addition of 1 M NaOH and
the organic materials were extracted with ether. The organic
layer was washed with 1 M NaOH and dried over Na2SO4.
The solvent was evaporated under reduced pressure and the
residue was purified by PTLC (hexane) to give 3a (56 mg,
88%; E/Z¼89:11).
4.2.5. 1-(Benzylthio)-2-phenylethene (3e)8 (E/Z¼90:10).
IR (neat): 3027, 1590, 1494, 1451, 935, 739, 712, 690;
1H NMR: 3.99 (s, 1.80H), 4.01 (s, 0.20H), 6.25 (d,
J¼11.0 Hz, 0.10H), 6.42 (d, J¼10.8 Hz, 0.10H), 6.52 (d, J¼
15.6 Hz, 0.90H), 6.71 (d, J¼15.6 Hz, 0.90H), 7.15–7.46 (m,
10H); 13C NMR: 37.3, 124.3, 125.6, 127.0, 127.3, 127.4,
127.9, 128.5, 128.6, 128.7, 128.8, 129.4, 136.9, 137.2.
4.2.6. 1-(4-Chlorophenylthio)-2-phenylethene (3f) (E/Z¼
87:13). IR (neat): 3080, 1474, 1445, 1393, 1096, 959, 953,
1
817, 741, 690; H NMR: 6.41 (d, J¼10.6 Hz, 0.13H), 6.62
(d, J¼10.6 Hz, 0.13H), 5.74 (d, J¼15.4 Hz, 0.87H), 5.82 (d,
J¼15.4 Hz, 0.87H), 7.17–7.54 (m, 9H); 13C NMR: 122.4,
125.1, 126.1, 127.3, 127.8, 128.0, 128.3, 128.7, 129.3,
130.9, 131.2, 137.7, 132.9, 133.8, 136.2. Anal. Calcd for
C14H11ClS: C, 68.14; H, 4.49. Found: C, 68.11; H, 4.56.
Typical procedure using p-chlorobenezenethiol or alkane-
thiols: cyclohexanethiol (4b) (0.97 M in DMF, 0.35 mL,
0.36 mmol) was added to sodium hydride (55 wt % in min-
eral oil, 20 mg, 0.45 mmol) under argon and the mixture
was stirred for 10 min at room temperature. Tetrakis(triethyl
phosphite)nickel(0) (11 mg, 0.015 mmol), DMF (0.3 mL),
and a THF (1.2 mL) solution of b-bromostyrene (2a)
(55 mg, 0.3 mmol) were successively added to the mixture,
which was stirred for 2.5 h at 50 ꢀC. The reaction was
quenched by the addition of 1 M KOH and the organic ma-
terials were extracted with ether. The organic layer was
washed with 1 M KOH and dried over Na2SO4. The solvent
was evaporated under reduced pressure and the residue was
purified by PTLC (hexane) to afford 3b (61 mg, 93%;
E/Z¼88:12).
4.2.7. 1-(Phenylthio)-1-octene (3g)8 (E/Z¼52:48). IR
(neat): 3006, 2925, 2855, 1584, 1478, 1465, 1440, 1090,
1
1025, 949, 738, 689; H NMR: 0.89 (t, J¼6.1 Hz, 3H),
1.20–1.50 (m, 8H), 2.17 (dt, J¼7.1, 7.0 Hz, 0.52H), 2.25
(dt, J¼7.1, 5.8 Hz, 0.48H), 5.83 (dt, J¼9.2, 7.2 Hz, 0.48H),
6.00 (dt, J¼15.0, 7.1 Hz, 0.52H), 6.13 (d, J¼14.8 Hz,
0.52H), 6.19 (d, J¼9.2 Hz, 0.48H), 7.14–7.37 (m, 5H); 13C
NMR: 14.1, 22.6, 28.8, 28.9, 29.0, 29.1, 31.6, 31.7, 33.1,
120.5, 122.5, 126.0, 126.1, 128.3, 128.7, 128.90, 128.92,
133.8, 137.9.
4.2.8. (E)-1-(tert-Butylthio)-1-octene (3h). IR (neat): 2925,
1
2856, 1457, 1364, 1161, 950; H NMR: 0.88 (t, J¼6.8 Hz,
4.2.1. 1-Phenyl-2-(phenylthio)ethene (3a)8 (E/Z¼89:11).
3H), 1.21–1.43 (m, 17H), 2.11 (dt, J¼6.7, 6.7 Hz, 2H),
5.89 (dt, J¼15.0, 6.8 Hz, 1H), 6.06 (dt, J¼14.7, 1.1 Hz,
1H); 13C NMR: 14.1, 22.6, 28.7, 29.1, 30.8, 31.6, 33.3,
43.5, 119.6, 138.2. Anal. Calcd for C12H24S: C, 71.93; H,
12.07. Found: C, 71.72; H, 12.24.
IR (neat): 3058, 3023, 1598, 1582, 1494, 1476, 1088, 1025,
1
945, 737, 691; H NMR: 6.50 (d, J¼10.8 Hz, 0.11H), 6.59
(d, J¼10.6 Hz, 0.11H), 6.73 (d, J¼15.4 Hz, 0.89H), 6.88 (d,
J¼15.4 Hz, 0.89H), 7.20–7.55 (m, 10H); 13C NMR: 123.3,
126.0, 126.9, 127.1, 127.16, 127.20, 127.6, 128.3, 128.65,
128.72, 129.0, 129.1, 129.8, 130.0, 131.8, 135.2, 136.5.
4.2.9. (E)-1-(Benzylthio)-1-octene (3i).8 IR (neat): 3064,
3029, 3005, 2925, 2854, 1495, 1454, 1236, 943, 698; H
1
4.2.2. 1-(Cyclohexylthio)-2-phenylethene (3b)8 (E/Z¼
88:12). IR (neat): 3022, 2928, 2852, 1597, 1570, 1446,
1266, 998, 939, 737, 691; H NMR: 1.19–1.53 (m, 5H),
NMR: 0.87 (t, J¼6.9 Hz, 3H), 1.15–1.38 (m, 8H), 2.03 (dt,
J¼6.7, 6.7 Hz, 2H), 3.83 (s, 2H), 5.67 (dt, J¼15.0, 7.2 Hz,
1H), 5.89 (d, J¼14.8 Hz, 1H), 7.18–7.36 (m, 5H); 13C
NMR: 14.1, 22.6, 28.6, 29.1, 31.6, 33.1, 37.6, 121.8, 127.0,
128.4, 128.8, 132.7, 137.9.
1
1.57–1.69 (m, 1H), 1.71–1.89 (m, 2H), 1.94–2.12 (m, 2H),
2.82–3.05 (m, 1H), 6.33 (d, J¼11.0 Hz, 0.12H), 6.43 (d,
J¼11.0 Hz, 0.12H), 6.56 (d, J¼15.6 Hz, 0.88H), 6.76 (d, J¼
15.6 Hz, 0.88H), 7.14–7.52 (m, 5H); 13C NMR (E-isomer):
25.6, 26.0, 33.6, 45.3, 124.0, 125.5, 126.9, 128.6, 137.1.
4.2.10. 1-(4-Chlorophenylthio)-1-octene (3j) (E/Z¼82:18).
1
IR (neat): 2955, 2926, 2855, 1475, 1094, 1012, 815; H
NMR: 0.87–0.91 (m, 3H), 1.18–1.49 (m, 8H), 2.13–2.27 (m,
2H), 5.86 (dt, J¼9.2, 7.3 Hz, 0.18H), 5.98–6.13 (m, 1.82H),
7.19–7.17 (m, 4H); 13C NMR: 14.1, 22.6, 28.8, 28.88, 28.93,
29.1, 31.59, 31.63, 33.1, 120.0, 121.8, 128.97, 129.0, 129.4,
129.8, 131.8, 132.0, 134.7, 135.1, 135.3, 138.9. Anal. Calcd
for C14H19ClS: C, 65.99; H, 7.52. Found: C, 66.09; H, 7.56.
4.2.3. 1-(Ethylthio)-2-phenylethene (3c)21 (E/Z¼91:9). IR
(neat): 3021, 2971, 2925, 1597, 1570, 1495, 1446, 1265,
937, 738, 691; H NMR: 1.36 (t, J¼7.4 Hz, 3H), 2.83 (q,
1
J¼7.4 Hz, 2H), 6.26 (d, J¼11.0 Hz, 0.09H), 6.46 (d,
J¼15.6 Hz, 1.00H), 6.73 (d, J¼15.6 Hz, 0.91H), 7.14–7.50

9986
Y. Yatsumonji et al. / Tetrahedron 62 (2006) 9981–9987
4.2.11. (E)-4-(Phenylthio)-4-octene (E-3k).22 IR (neat):
3072, 2958, 2930, 2871, 1583, 1476, 1463, 1439, 740, 690;
1H NMR: 0.86 (t, J¼7.3 Hz, 3H), 0.94 (t, J¼7.4 Hz, 3H),
1.38–1.57 (m, 4H), 2.09–2.19 (m, 4H), 5.88 (t, J¼7.4 Hz,
1H), 7.14–7.33 (m, 5H); 13C NMR: 13.7, 13.8, 21.7, 22.7,
31.2, 33.0, 126.1, 128.8, 129.8, 133.5, 136.0, 137.4.
4H), 2.73 (t, J¼7.6 Hz, 4H), 7.16–7.31 (m, 10H); 13C
NMR: 18.2, 30.7, 34.8, 90.3, 125.8, 128.3, 128.5, 141.8.
4.2.19. Cyclohexyl phenyl sulfide (10a).8 IR (neat): 3053,
2972, 2925, 1564, 1502, 1262, 976, 788, 769; H NMR:
1
1.15–1.45 (m, 5H), 1.51–1.66 (m, 1H), 1.69–1.85 (m, 2H),
1.89–2.06 (m, 2H), 3.11 (tt, J¼10.4, 3.7 Hz, 1H), 7.17–
7.32 (m, 3H), 7.36–7.42 (m, 2H); 13C NMR: 25.7, 26.0,
33.3, 46.5, 126.6, 128.7, 131.8, 135.1.
4.2.12. (Z)-4-(Phenylthio)-4-octene (Z-3k). IR (neat):
2958, 2924, 2871, 1583, 1476, 1463, 740, 691; H NMR:
1
0.82 (t, J¼7.4 Hz, 3H), 0.93 (t, J¼7.3 Hz, 3H), 1.37–1.53
(m, 4H), 2.13 (t, J¼7.3 Hz, 2H), 2.32 (dt, J¼7.3, 7.3 Hz,
2H), 5.91 (t, J¼7.1 Hz, 1H), 7.12–7.26 (m, 5H); 13C NMR:
13.3, 13.8, 21.5, 22.7, 31.9, 39.6, 125.6, 128.7, 129.1,
132.9, 136.8.
4.2.20. Diphenyl sulfide (10b).8 IR (neat): 3059, 1579,
1475, 1439, 1080, 1024, 737, 688; H NMR: 7.21–7.49
1
(m, 10H); 13C NMR: 127.0, 129.2, 131.0, 135.8.
4.2.21. Benzyl phenyl sulfide (10c).8 IR (neat): 3058, 3046,
1480, 1454, 1438, 730, 715, 686; H NMR: 4.12 (s, 2H),
1
4.2.13. (E)-4-(tert-Butylthio)-4-octene (3l). IR(neat): 2959,
2871, 1457, 1378, 1362, 1164, 1148, 900; 1H NMR: 0.89 (t,
J¼7.2 Hz, 3H), 0.93 (t, J¼7.1 Hz, 3H), 1.31 (s, 9H), 1.33–
1.58 (m, 4H), 2.10 (dt, J¼7.2, 7.5 Hz, 2H), 2.26 (t, J¼
7.5 Hz, 2H), 5.93 (t, J¼7.5 Hz, 1H); 13C NMR: 13.7, 13.8,
21.8, 22.7, 31.38, 31.44, 36.8, 45.4, 133.1, 142.9. Anal. Calcd
for C12H26S: C, 71.21; H, 12.95. Found: C, 71.64; H, 12.63.
7.10–7.30 (m, 10H); 13C NMR: 39.0, 126.3, 127.1, 128.5,
128.79, 128.81, 129.8.
4.2.22. 4-Chlorophenyl phenyl sulfide (10d).18 IR (neat):
1475, 1094, 952, 820, 741, 690; H NMR: 7.20–7.35 (m,
1
9H); 13C NMR: 127.4, 129.29, 129.32, 131.3, 132.0,
133.0, 134.6, 135.1.
4.2.14. 4-(tert-Butylthio)-1,8-diphenyl-4-octene (3m). IR
(neat): 3026, 2936, 2857, 1496, 1454, 1362, 1162, 746,
4.2.23. Ethyl naphthyl sulfide (10e).24 IR (neat): 3072,
2928, 2852, 1583, 1479, 1447, 750, 735, 691; H NMR:
1.33 (t, J¼7.4 Hz, 3H), 3.01 (q, J¼7.4 Hz, 2H), 7.41 (dd,
J¼7.2, 8.1 Hz, 1H), 7.47–7.58 (m, 3H), 7.73 (d, J¼8.4 Hz,
1H), 7.85 (d, J¼7.5 Hz, 1H), 8.40 (d, J¼7.8 Hz, 1H); 13C
NMR: 14.4, 28.2, 125.0, 125.5, 126.1, 126.2, 126.9, 127.7,
128.5.
1
1
698; H NMR: 1.29 (s, 9H), 1.70 (tt, J¼7.5, 7.5 Hz, 2H),
1.83 (tt, J¼7.7, 7.7 Hz, 2H), 2.09 (dt, J¼4.4, 7.4 Hz, 2H),
2.28 (t, J¼7.5 Hz, 2H), 2.58 (t, J¼8.0 Hz, 2H), 2.60 (t,
J¼7.8 Hz, 2H), 5.96 (t, J¼7.4 Hz, 1H), 7.10–7.32 (m,
10H); 13C NMR: 28.9, 30.1, 31.2, 31.4, 34.2, 35.4, 35.5,
45.5, 125.6, 125.8, 128.2, 128.3, 128.4, 128.4, 133.5,
142.1, 142.3, 142.4. Anal. Calcd for C24H32S: C, 81.76; H,
9.15. Found: C, 82.12; H, 9.49.
4.3. In situ oxidation of the alkenyl sulfides 3
4.2.15. (E)-1-(Phenylthio)-1-(trimethylsilyl)-1-octene
(3n). IR (neat): 3072, 3060, 1585, 1476, 1439, 1247, 837,
Typical procedure: the alkenyl sulfide 3a was prepared in the
dark in a similar manner as described above. After comple-
tion of the reaction, the reaction mixture was cooled to 0 ꢀC.
A CH2Cl2 (2.7 mL) solution of MCPBA (672 mg, 3.0 mmol)
was added and the reaction mixture was stirred for 11 h in
the dark. The reaction was quenched by the addition of
1 M NaOH and the organic materials were extracted with
CH2Cl2. The organic layer was washed with 1 M NaOH
and dried over Na2SO4. The solvent was evaporated under
reduced pressure and the residue was purified by PTLC (hex-
ane/EtOAc¼2:1, v/v) to give 5a (64 mg, 93%).
4.3.1. (E)-1-Phenyl-2-(phenylsulfinyl)ethene (5a).25 IR
(neat): 3058, 3025, 1494, 1476, 1084, 1045, 998, 739, 689;
1H NMR: 6.84 (d, J¼15.6 Hz, 1H), 7.30–7.56 (m, 9H),
7.64–7.72 (m, 2H); 13C NMR: 124.7, 127.8, 128.9, 129.4,
129.9, 131.1, 133.0, 133.7, 136.4, 143.9.
1
738, 690; H NMR: 0.21 (s, 9H), 1.05 (t, J¼6.8 Hz, 3H),
1.36–1.65 (m, 8H), 2.57 (dt, J¼7.7, 6.9 Hz, 2H), 6.77 (t,
J¼6.8 Hz, 1H), 7.23–7.44 (m, 5H); 13C NMR: ꢁ1.2, 14.0,
22.6, 28.8, 29.0, 30.9, 31.6, 124.9, 127.8, 128.5, 133.1,
138.0, 153.5. Anal. Calcd for C17H28SSi: C, 69.79; H,
9.65. Found: C, 69.36; H, 9.79.
4.2.16. (E)-1-(4-Chlorophenylthio)-1-(trimethylsilyl)-1-
octene (3o). IR (neat): 2956, 2925, 2855, 1474, 1247,
1
1092, 837, 815; H NMR: 0.20 (s, 9H), 1.03 (t, J¼6.8 Hz,
3H), 1.32–1.63 (m, 8H), 2.53 (dt, J¼7.5, 7.1 Hz, 2H), 6.77
(t, J¼6.8 Hz, 1H), 7.26 (d, J¼6.8 Hz, 2H), 7.35 (d,
J¼6.6 Hz, 2H); 13C NMR: ꢁ1.2, 14.0, 22.6, 28.7, 29.0,
31.0, 31.6, 128.6, 128.7, 130.6, 132.8, 136.7, 154.2. Anal.
Calcd for C17H27ClSSi: C, 62.44; H, 8.32. Found: C, 62.59;
H, 8.56.
4.3.2. (E)-1-(Phenylsulfinyl)octene (5b).25 IR (neat): 2926,
2855, 1466, 1443, 1085, 1046, 958, 920, 746; 1H NMR: 0.87
(t, J¼6.8 Hz, 3H), 1.16–1.37 (m, 6H), 1.46 (tt, J¼7.4 Hz,
2H), 2.23 (dt, J¼7.2, 7.2 Hz, 2H), 6.23 (dt, J¼15.0,
1.4 Hz, 1H), 6.62 (dt, J¼15.0, 6.8 Hz, 1H), 7.43–7.54 (m,
3H), 7.59–7.63 (m, 2H); 13C NMR: 14.0, 22.5, 28.0, 28.7,
31.5, 32.0, 124.4, 129.2, 130.8, 134.9, 141.6, 144.3.
4.2.17. 3-Benzyl-4-phenyl-1-butyne (7a). IR (neat): 3293,
3062, 3028, 2923, 1496, 1454, 752, 735, 699; H NMR:
2.05 (d, J¼2.4 Hz, 1H), 2.74–2.82 (m, 4H), 2.89–2.95 (m,
1H), 7.19–7.31 (m, 10H); 13C NMR: 35.4, 40.6, 71.0,
86.5, 126.4, 128.2, 129.2, 139.1. Anal. Calcd for C17H16:
C, 92.68; H, 7.32. Found: C, 92.63; H, 7.31.
1
4.2.18. 1,8-Diphenyl-4-octyne (7b).23 IR (neat): 3084,
3061, 3026, 2938, 2858, 1603, 1496, 1454, 1433, 745,
699; H NMR: 1.82 (tt, J¼7.3 Hz, 4H), 2.19 (t, J¼7.0 Hz,
4.3.3. (E)-1-(Ethylsulfonyl)-2-phenylethene (6).21 IR
(neat): 3054, 2979, 1616, 1450, 1304, 1126, 979, 856, 822,
747, 688; 1H NMR: 1.40 (t, J¼7.4 Hz, 3H), 3.10 (q,
1

Y. Yatsumonji et al. / Tetrahedron 62 (2006) 9981–9987
9987
12. (a) Fujiwara, T.; Yanagihara, H.; Yamada, T.; Takeda, T. Chem.
Lett. 1985, 15, 1629; (b) Takeda, T.; Kanamori, F.; Masuda, M.;
Fujiwara, T. Tetrahedron Lett. 1991, 32, 5567.
J¼7.5 Hz, 2H), 6.82 (d, J¼15.6 Hz, 1H), 7.39–7.48 (m, 3H),
7.48–7.57 (m, 2H), 7.61 (d, J¼14.4 Hz, 1H); 13C NMR: 7.3,
49.4, 123.9, 128.5, 129.1, 131.4, 132.2, 145.2.
13. When a similar oxidation was performed after the Ni(0) cata-
lyzed formation of alkenyl sulfide 3a without light shielding,
both E- and Z-isomers of the corresponding sulfoxide 5a
were obtained (E/Z¼95:5) in 90% yield.
Acknowledgements
14. Lin, B.-L.; Liu, L.; Fu, Y.; Luo, S.-W.; Chan, Q.; Guo, Q.-X.
Organometallics 2004, 23, 2114.
This work was carried out under the 21st Century COE
program of ‘Future Nano-materials’ in Tokyo University
of Agriculture and Technology.
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