Stereoselective synthesis of trisubstituted alkenes containing (Z)-allylthio units from the acetates of Baylis-Hillman adducts

Article abstract of DOI:10.1002/hc.20394

A series of trisubstituted alkenes containing (Z)-allylthio moieties as key structural units, that is, sodium (Z)-allyl thiosulfates, symmetrical di(Z-allyl) sulfides, and di(Z-allyl) disulfides, unsymmetrical diallyl sulfides were prepared in moderate to

Full text of DOI:10.1002/hc.20394

Heteroatom Chemistry
Volume 19, Number 2, 2008
Stereoselective Synthesis of Trisubstituted
Alkenes Containing (Z)-Allylthio Units
from the Acetates of Baylis–Hillman Adducts
Yunkui Liu,1 Danqian Xu,1 Zhenyuan Xu,1 and Yongmin Zhang2
1State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology,
Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
2Department of Chemistry, Zhejiang University, Xi-xi Campus, Hangzhou 310028,
People’s Republic of China
Received 6 January 2007; revised 10 April 2007
have been developed for the stereoselective synthesis
ABSTRACT: A series of trisubstituted alkenes
of trisubstituted alkenes [2,3]. In view of their signifi-
containing (Z)-allylthio moieties as key structural
cance in organic synthesis and potential bioactivity,
units, that is, sodium (Z)-allyl thiosulfates, sym-
it is still desirable to extend the scope of trisubsti-
metrical di(Z-allyl) sulfides, and di(Z-allyl) disul-
tuted alkene family and develop new and convenient
fides, unsymmetrical diallyl sulfides were prepared
synthetic routes.
in moderate to good yields via chemical transforma-
The Baylis–Hillman reaction is well known
tions from the acetates of Baylis–Hillman adducts.
as a powerful carbon–carbon bond-forming reac-
ꢀ
C
2008 Wiley Periodicals, Inc. Heteroatom Chem 19:188–
tion providing synthetically useful multifunctional
adducts [4]. These adducts have been widely utilized
as useful precursors for stereoselective synthesis of
198, 2008; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20394
various trisubstituted alkenes [4,5].
Organosulfur compounds possessing allylthio
moieties serve as important building blocks in or-
ganic synthesis [6–9] and have potential bioactivity
INTRODUCTION
Trisubstituted alkenes have received much attention
as a class of important compounds in organic syn-
thesis because such moieties manifested a signifi-
cant role in many biologically active compounds,
such as terpenoids, insect pheromones, and antibi-
otics and so on [1]. The biological properties of these
alkenes are highly dependent on the configuration of
the C C bonds [2]. Therefore, a number of methods
[10]. As our interest in conversion of Baylis–Hillman
adducts into trisubstituted alkenes [11], we herein
report the results on the stereoselective synthesis of
a series of trisubstituted alkenes containing allylthio
moieties, that is, sodium (Z)-allyl thiosulfates, sym-
metrical di(Z-allyl) sulfides, and di(Z-allyl) disul-
fides, unsymmetrical diallyl sulfides, via chemical
transformations from the acetates of Baylis–Hillman
adducts (derived from acrylate esters). A part of
preliminary results have been published [12]. Some
allyl sulfide analogs prepared from Baylis–Hillman
alcohols or Baylis-Hillman bromides by other ap-
proaches have been previously reported in the liter-
ature [13].
Correspondence to: Zhenyuan Xu; e-mail: greensyn@zjut.
edu.cn.
Contract grant sponsor: The Opening Foundation of Zhejiang
Provincial Top Key Discipline.
c
ꢀ
2008 Wiley Periodicals, Inc.
188

Stereoselective Synthesis of Trisubstituted Alkenes Containing (Z )-Allylthio Units 189
TABLE 1 Preparation of Sodium (Z)-Allyl Thiosulfates 2 from
the Baylis–Hillman Acetates 1a
RESULTS AND DISCUSSION
Synthesis of Sodium(Z)-allyl Thiosulfates and
Symmetrical DI(Z-allyl) Sulfides
Product
Time Yield c
Entry R
(2)b Solvent (h)
(%)
At the beginning of this study, synthesis of sodium
(Z)-allyl thiosulfates (Baylis–Hillman adduct-
derived Bunte salts) was tried. Treatment of
Baylis–Hillman acetates 1 with sodium thiosulfate
pentahydrate in anhydrous methanol at room
temperature afforded the corresponding Bunte
salts 2 in almost quantitative yields (Scheme 1 and
Table 1).
A series of solvents were tested to optimize the
reaction conditions (Table 1, entry 1 and 2). When
Et2O, CH2Cl2, THF, and CH3CN were used as sol-
vent, the reaction proceeded slowly and gave poor
yields of products; fairly good yield was obtained
in DMF, whereas the best result was found in an-
hydrous MeOH. A variety of substrates were used
in this reaction to establish the generality and effi-
ciency, and all reactions proceeded smoothly under
similar conditions. The experimental results showed
that the present method was effective for substrates
possessing either aryl groups (Table 1, entries 2–10)
or alkyl ones (Table 1, entries 11 and 12). Among
substrates bearing aryl groups, those containing
electron-withdrawing functionalities reacted more
slowly and gave slightly reduced yields of products
(Table 1, entry 9).
1
C6H5 (1a)
2a
Et2O
CH2Cl2 4.0
THF 4.0
CH3CN 4.0
DMF 4.0
MeOH 4.0
MeOH 4.0
MeOH 4.0
MeOH 4.0
MeOH 4.0
MeOH 4.0
MeOH 4.0
MeOH 8.0
MeOH 4.0
MeOH 5.0
MeOH 5.0
4.0
30
45
38
52
84
97
98
95
94
97
96
95
93
95
94
92
2
3
4
5
6
7
8
9
C6H5 (1a)
4-CH3C6H4 (1b)
4-ClC6H4 (1c)
2-ClC6H4 (1d)
4-CH3OC6H4 (1e)
2-CH3OC6H4 (1f)
3,4-OCH2OC6H3 (1g)
2-NO2C6H4 (1h)
2-Furyl (1i)
2a
2b
2c
2d
2e
2f
2g
2h
2i
10
11
12
C6H5CH2CH2 (1j)
n-C7H15 (1k)
2j
2k
aReagents and conditions: 1 (1 mmol), Na2SSO3·5H2O (1 mmol),
MeOH (15 mL), room temperature, 4.0–8.0 h.
bAll new products were characterized by 1H NMR, MS, IR, and ele-
mental analysis.
cIsolated yields.
The reactions exhibited high stereoselectivity.
In all cases, the allylthio moieties in 2 took a Z
configuration. The Z configuration of the products
was assigned by comparing the chemical shifts in
1H NMR with reported relevant values of trisubsti-
tuted alkenes. According to the reports published in
SCHEME 2
Encouraged by the successful synthesis of 2 from
1 and Na2SSO3·5H2O, we expected that symmetrical
diallyl sulfides would be obtained if 1 would be al-
lowed to react with Na2S. Indeed, when 1 equivalent
of 1 was treated with 0.55 equivalent of Na2S·9H2O
in anhydrous methanol under similar reaction con-
ditions, symmetrical di(Z-allyl) sulfides 3 were pro-
duced in high yields (Scheme 2 and Table 2). It was
found that the required reaction time, effect of sub-
stituted groups, and stereoselectivity of the reaction
were similar to the cases in the reaction of 1 with
Na2SSO3·5H2O.
1
the literature, in the H NMR spectrum of a trisub-
stituted alkene the β-vinylic proton, cis- and trans-
to the ester group are known to resonate at δ 7.5 and
δ 6.5, respectively, when alkene is substituted by an
aryl group; whereas the same proton cis- and trans-
to an ester group appears at δ 6.8 and δ 5.7, respec-
tively, when substituted by an alkyl one [14]. It was
finally confirmed by NOESY experiments. According
to these experiments, there is no NOE correlation be-
tween the signal of the internal olefin proton and the
allylic methylene protons.
Synthesis of Unsymmetrical Diallyl Sulfides
With sodium (Z)-allyl thiosulfates were in hand, we
next investigated whether the in situ prepared Bunte
salts 2 could be used as intermediates for further
transformations without purification, since the pro-
cess showed very clean conversion, thus giving op-
portunities to synthesize other advanced molecules
in convenient one-pot manner. For the initial try,
SCHEME 1
Heteroatom Chemistry DOI 10.1002/hc

190 Liu et al.
TABLE 2 Preparation of Symmetrical Di(Z-allyl) Sulfides 3
from the Baylis–Hillman Acetates 1a
TABLE 3 Preparation of Unsymmetrical Diallyl Sulfides 4
from the Allylic Acetates 1, Na2SSO3·5H2O, and Allyl Bro-
mide Promoted by Indiuma
Product
Time
(h)
Yieldc
(%)
Entry
R
(3)b
Product Time
Yieldd
(%)
Entry
1
R
(4)b
(h)c
1
2
3
4
5
6
7
8
C6H5 (1a)
3a
3b
3c
3d
3f
3g
3h
3i
3.0
3.0
3.0
3.0
3.0
3.0
6.0
3.0
5.0
5.0
5.0
94
95
91
92
90
90
89
91
90
88
87
4-CH3C6H4 (1b)
4-ClC6H4 (1c)
2-ClC6H4 (1d)
2-CH3OC6H4 (1f)
3,4-OCH2OC6H3 (1g)
2-NO2C6H4 (1h)
2-Furyl (1i)
C6H5 (1a)
4a
8.0
75
0e
38f
76
74
58
67
65
63
64
68
63
61
2
3
4
5
6
7
8
9
4-CH3C6H4 (1b)
4-ClC6H4 (1c)
4b
4c
4d
4e
4f
4g
4h
4i
8.0
8.0
8.0
8.0
8.0
8.0
8.0
8.0
12.0
12.0
2-ClC6H4 (1d)
4-CH3OC6H4 (1e)
2-CH3OC6H4 (1f)
3,4-OCH2OC6H3 (1g)
2-NO2C6H4 (1h)
2-Furyl (1i)
C6H5CH2CH2 (1j)
n-C7H15 (1k)
9
10
11
C6H5CH2CH2 (1j)
n-C7H15 (1k)
Et (1l)
3j
3k
3l
aReagents and conditions: 1 (1 mmol), Na2S·9H2O (0.55 mmol),
MeOH (15 mL), room temperature, 3.0–6.0 h.
bAll new products were characterized by 1H NMR, MS, IR, and ele-
mental analysis.
10
11
4j
4k
aReagents and conditions: 1 (1 mmol), Na2SSO3·5H2O (1 mmol),
MeOH (15 mL), room temperature., 4.0–8.0 h, then allyl bromide
(3 mmol), In (1.5 mmol), 55◦C, 8.0–12.0 h.
cIsolated yields.
bAll products were characterized by 1H NMR, MS, IR, and elemental
analysis.
indium-mediated reaction [15] of allyl bromide with
2 was tested. Successfully, the reaction afforded un-
symmetrical diallylsulfides 4 in moderate to good
yields (Scheme 3 and Table 3).
cTime needed for indium-mediated allylation.
dIsolated yields.
eIndium-mediated allylation was carried out at room temperature.
f 1 mmol allyl bromide and 1 mmol indium were used.
The indium-mediated allylation of 2 proceeded
smoothly at 55◦C, whereas no reaction occurred at
room temperature (Table 3, entry 1). To obtain de-
sirable yield of products, using excessive amount
of allyl bromide (3 equivalents) and indium (1.5
equivalents) was necessary for the reaction (Table 3,
entry 1). The generality of the reaction was estab-
lished by examining various substrates. The acetates
of Baylis–Hillman alcohols having either aryl (with
electron-donating as well as electron-withdrawing
functionalities) or alkyl groups could be converted to
the corresponding unsymmetrical diallylsulfides in
moderate to good yields. Upon formation of 4, the Z
configuration of the allylthio moiety in 2 was entirely
conserved. Besides, the reaction exhibited excellent
regioselectivity. Only S-allylated products 4 were ob-
tained, whereas no 1,4- or 1,2-allylated derivatives
were detected if taking 2 as α,β-unsaturated car-
bonyl compounds.
SCHEME 3
Heteroatom Chemistry DOI 10.1002/hc

Stereoselective Synthesis of Trisubstituted Alkenes Containing (Z )-Allylthio Units 191
TABLE 4 Preparation of Symmetrical Di(Z-allyl) Disulfides
5 or Methyl Cinnamic Esters 6a
potential bioactive compounds [6,10]. Encouraged
by the successful synthesis of 4 from the in situ
prepared 2, we further wanted to obtain symmet-
rical diallyl disulfides in one-pot strategy by treat-
ment of 2 with a Sm/I2(trace) system under aque-
ous media [16]. Interestingly, selective cleavage
of the S S or C S bonds in Bunte salts 2 was
achieved to form corresponding di(Z-allyl) disulfides
or methyl cinnamic esters in moderate to good yields
(Scheme 3 and Table 4). Thus, when 2 derived from
those alkyl-substituted 1 was used as substrates, the
reaction proceeded smoothly and gave di(Z-allyl)
disulfides 5 in moderate to good yields (Table 3,
entries 1–3). However, when 2 derived from those
aryl-substituted 1 was allowed to react in the same
conditions, selective cleavage of the C S bonds
predominated to give methyl cinnamic esters 6
(methyl cinnamic eaters prepared from Baylis–
Hillman adducts or derivatives by other approaches,
see [17]) in moderate to good yields whereas di(Z-
allyl) disulfides 5 from the cleavage of the S S bonds
were only obtained in very less amount (Table 3,
entries 4–9).
Yieldc (%)
Entry
R
Time (h)b
5d
6d
e
e
e
1
2
3
4
5
6
7
8
9
C6H5CH2CH2 (1j)
n-C7H15 (1k)
3.0
3.0
3.0
4.0
4.0
4.0
4.0
4.0
4.0
84 (5j)
82 (5k)
74 (5l)
<5
–
–
–
Et (1l)
C6H5 (1a)
83 (6a)
85 (6b)
Trace 84 (6c)
Trace 80 (6d)
4-CH3C6H4 (1b)
4-ClC6H4 (1c)
2-ClC6H4 (1d)
2-CH3OC6H4 (1f)
3,4-OCH2OC6H3 (1g)
<5
<7
<5
78 (6f)
77 (6g)
aReagents and conditions: 1 (1 mmol), Na2SSO3·5H2O (1 mmol),
MeOH (15 mL), room temperature, 4.0–8.0 h, then samarium
(1 mmol), I2 ( trace), THF (20 mL), NH4Cl saturated solution (4 mL),
room temperature, 3.0–4.0 h.
bTime needed for Sm/I2(trace) system-mediated reduction.
cIsolated yields.
dAll new products were characterized by 1H NMR, MS, IR, and ele-
mental analysis.
eNot detected.
Synthesis of Symmetrical Diallyl Disulfides or
Methyl Cinnamic Esters via Selective Cleavage
of S S or C S bonds in 2 Promoted by a Sm/I2
(trace) System
A possible mechanism for the selective cleavage
of the S S or C S bonds in 2 is depicted in Scheme 4.
Perhaps the samarium powder was activated by I2
and aqueous NH4Cl [16b,18], thus an electron was
transferred to the substrate 2 to form the radical
Diallyl disulfides are a class of useful and impor-
tant building blocks in organic synthesis as well as
SCHEME 4
Heteroatom Chemistry DOI 10.1002/hc

192 Liu et al.
anion 7 [19]; when R was an alkyl group, selective
cleavage of the S S bond occurred to form S-radical
intermediate 8, which then dimerized to afford the
di(Z-allyl) disulfide 5; but when R was an aryl group,
cleavage of the C S bond may be predominated to
give allyl radical species 9 or 10. Then, 9 received
another electron from Sm to produce allyl anion in-
termediate 11. Here, the attached aryl group in the
allyl moiety may be capable of stabilizing the allyl
anion, so that the methyl cinnamic ester 6 could be
formed by protonation of the intermediate 11.
at room temperature for 4–8 h. Then to the resul-
tant mixture, silica gel powder (2.0 g) was added. Af-
ter evaporation of solvent, we got silica gel-absorbed
powder of crude product, which was loaded to chro-
matography column for further purification using
MeOH-EtOAc (1:1) as eluent.
Compound 2a. White solid. mp 106–108◦C; IR
(KBr): 3082, 3026, 1714 (C O), 1625 (C C), 1250,
1147 (SO−3 ) cm−1; 1H NMR (DMSO-d6, 400 MHz)
δ: 3.71 (s, 3H, OCH ), 4.05 (s, 2H, methylene-
3
H), 7.38–7.46 (m, 3H, ArH), 7.63 (s, 1H, ArCH ),
7.67–7.72 (m, 2H, ArH); 13C NMR (d6-DMSO, 100
MHz) δ 31.49, 52.35, 127.33, 128.86, 129.56, 130.42,
134.24, 140.77, 167.28; EI-MS (70 eV) m/z: 207 (M+
−SO3Na); Anal. Calcd for C11H11NaO5S2: C 42.57; H
3.57. Found: C 42.89; H 3.65.
CONCLUSION
In summary, a series of trisubstituted alkenes con-
taining Z-allylthio moieties as the key structural
units were prepared in moderate to good yields
via chemical transformations from the acetates of
Baylis–Hillman adducts. These compounds included
sodium (Z)-allyl thiosulfates, symmetrical di(Z-allyl)
sulfides and di(Z-allyl) disulfides, and unsymmetri-
cal diallyl sulfides. Besides, it was found that the Sm
and a trace amount of I2 system could be used for
the selective cleavage of the S S or C S bonds in
sodium (Z)-allyl thiosulfates depending on the sub-
stituents (alkyl or aryl group) to give the correspond-
ing di(Z-allyl) disulfides or methyl cinnamic esters,
respectively. The notable advantages of these reac-
tions were easy availability of the starting materials,
high stereoselectivity and/or regioselectivity, simple
one-pot operation, and mild reaction conditions.
Compound 2b. White solid. mp 200–202◦C; IR
(KBr): 3078, 3022, 1720 (C O), 1624 (C C), 1210,
1164 (SO3−) cm−1;1H NMR (DMSO-d6, 400 MHz) δ:
2.35 (s, 3H, CH ), 3.76 (s, 3H, OCH ), 4.05 (s, 2H,
3
3
methylene-H), 7.26 (d, 2H, J = 8.0 Hz, ArH), 7.62–
7.65 (m, 3H, ArH overlapped with ArCH ); 13C NMR
(d6-DMSO, 100 MHz) δ: 21.0, 31.43, 52.18, 126.24,
129.40, 130.48, 131.41, 139.35, 140.74, 167.26;
EI-MS (70 eV) m/z: 221 (M+−SO3Na); Anal. Calcd
for C12H13NaO5S2: C 44.44; H 4.04. Found: C 44.76;
H 3.96.
Compound 2c. White solid. mp 168–170◦C; IR
(KBr): 3083, 3020, 1713 (C O), 1627 (C C), 1214,
EXPERIMENTAL
General
1164 (SO3−) cm−1; H NMR (DMSO-d6, 400 MHz)
1
δ: 3.78 (s, 3H, OCH ), 4.04 (s, 2H, methylene-H),
3
7.50 (d, 2H, J = 8.8 Hz, ArH), 7.65 (s, 1H, ArCH ),
7.77 (d, 2H, J = 8.8 Hz, ArH); 13C NMR (d6-DMSO,
100 MHz) δ: 30.84, 52.33, 128.23, 128.73, 132.13,
133.12, 134.11, 139.21, 167.01; EI-MS (70 eV) m/z:
241 (35Cl M+−SO3Na), 243 (37Cl M+−SO3Na); Anal.
Calcd for C11H10ClNaO5S2: C 38.32; H 2.92. Found:
C 38.60; H 2.98.
Melting points are uncorrected. IR spectra were
recorded on a Bruker Victor 22 spectrometer.
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra
were recorded on a Bruker AC-400 spectrometer for
solutions in CDCl3 or DMSO-d6 with TMS as internal
standard. Chemical shifts (δ) are expressed in ppm,
and coupling constants J are given in hertz. Mass
spectra were obtained on a HP 5989B mass spec-
trometer. Elemental analyses were performed on
a EA-1110 instrument. All Baylis–Hillman acetates
were prepared according to the reported methods in
the literature [20].
Compound 2d. White solid. mp 213–215◦C; IR
(KBr): 3080, 3020, 1713 (C O), 1629 (C C), 1212,
1166 (SO−3 ) cm−1; 1H NMR (DMSO-d6, 400 MHz)
δ: 3.63 (s, 3H, OCH ), 3.78 (s, 2H, methylene-
3
H), 7.23–7.32 (m, 2H, ArH), 7.37–7.41 (m, 1H,
ArH), 7.55 (s, 1H, ArCH ), 7.72–7.75 (m, 1H,
ArH); 13C NMR (d6-DMSO, 100 MHz) δ: 31.85,
53.36, 128.23, 129.95, 130.24, 131.38, 131.76, 132.85,
134.10, 138.17, 167.57; EI-MS (70 eV) m/z: 241
(35Cl M+−SO3Na), 243 (37Cl M+−SO3Na); Anal.
Calcd for C11H10ClNaO5S2: C 38.32; H 2.92. Found:
C 38.03; H 2.96.
General Procedure for Preparation of Sodium
(Z)-Allyl Thiosulfates 2 from the Baylis–Hillman
Acetates 1 and Sodium Thiosulfate Pentahydrate
In a 25-mL flask, Na2SSO3·5H2O (0.25 g, 1 mmol),
Baylis–Hillman acetate 1 (1 mmol), and anhydrous
MeOH (15 mL) were added. The mixture was stirred
Heteroatom Chemistry DOI 10.1002/hc

Stereoselective Synthesis of Trisubstituted Alkenes Containing (Z )-Allylthio Units 193
Compound 2e. White solid. mp 180–182◦C; IR
(DMSO-d6, 100 MHz) δ: 32.03, 53.20, 113.97, 118.41,
123.28, 128.50, 146.89, 150.40, 168.0; EI-MS (70 eV)
m/z: 197 (M+−SO3Na); Anal. Calcd for C9H9NaO6S2:
C 36.00; H 3.02. Found: C 36.26; H 2.95.
(KBr): 30−71, 3018, 1708 (C O), 1626 (C C), 1242,
1
1128 (SO3 ) cm−1; H NMR (DMSO-d6, 400 MHz) δ:
3.76 (s, 3H, OCH ), 3.83 (s, 3H, OCH ), 4.08 (s, 2H,
3
3
methylene-H), 7.01 (d, 2H, J = 8.8 Hz, ArH), 7.63 (s,
1H, ArCH ), 7.75 (d, 2H, J = 8.8 Hz, ArH); 13C NMR
(d6-DMSO, 100 MHz) δ: 32.33, 53.10, 56.05, 115.06,
124.20, 127.12, 133.28, 142.12, 161.10, 168.38;
EI-MS (70 eV) m/z: 237 (M+−SO3Na); Anal. Calcd
for C12H13NaO6S2: C 42.35; H 3.85. Found: C 42.70;
H 3.76.
Compound 2j. White solid. mp 73–75◦C; IR
(KBr): 1709 (C O), 1619 (C C), 1297, 1201 (SO−3 )
cm−1; 1H NMR (DMSO-d6, 400 MHz) δ: 2.48 (q,
2H, J = 7.0 Hz), 2.63 (t, 2H, J = 7.0 Hz), 3.66
(s, 3H, OCH ), 4.05 (s, 2H), 6.79 (t, 1H, J = 7.0
3
Hz, alkyl-CH ), 7.10–7.15 (m, 3H, ArH), 7.20–7.24
(m, 2H, ArH); 13C NMR (d6-DMSO, 100 MHz) δ:
29.95, 30.25, 34.03, 51.90, 126.08, 128.43, 128.50,
128.88, 141.25, 144.36, 166.64; EI-MS (70 eV) m/z:
235 (M+−SO3Na); Anal. Calcd for C13H15NaO5S2: C
46.14; H 4.47. Found: C 46.38; H 4.39.
Compound 2f. White solid. mp 62–64◦C; IR
(KBr): 3074, 3022, 1709 (C O), 1627 (C C), 1246,
1164 (SO−3 ) cm−1; 1H NMR (DMSO-d6, 400 MHz)
δ: 3.77 (s, 3H, OCH ), 3.85 (s, 3H, OCH ), 4.03 (s,
3
3
2H, methylene-H), 6.98–7.12 (m, 2H, ArH), 7.41–
7.46 (m, 1H, ArH), 7.83–7.86 (m, 2H, ArH over-
lapped with ArCH ); 13C NMR (d6-DMSO, 100
MHz) δ: 32.25, 53.05, 56.28, 111.79, 121.29, 123.18,
127.01, 130.62, 132.18, 137.32, 158.21, 168.09;
EI-MS (70 eV) m/z: 237 (M+−SO3Na); Anal. Calcd
for C12H13NaO6S2: C 42.35; H 3.85. Found: C 42.78;
H 3.77.
Compound 2k. White solid. mp 104–106◦C; IR
(KBr): 1708 (C O), 1618 (C C), 1276, 1219 (SO−3 )
1
cm−1; H NMR (DMSO-d6, 400 MHz) δ: 0.86 (t, 3H,
J = 6.8 Hz), 1.26–1.42 (m, 10H), 2.30 (q, 2H, J = 7.5
Hz), 3.66 (s, 3H, OCH ), 3.78 (s, 2H), 6.73 (t, 1H,
3
J = 7.5 Hz, alkyl-CH ); 13C NMR (d6-DMSO, 100
MHz) δ: 14.60, 22.83, 28.82, 28.98, 29.27, 29.46,
30.48, 31.96, 52.70, 128.29, 147.10, 167.53; EI-MS
(70 eV) m/z: 229 (M+−SO3Na); Anal. Calcd for
C12H21NaO5S2: C 43.36; H 6.37. Found: C 43.70;
H 6.29.
Compound 2g. White solid. mp 192–194◦C; IR
(KBr): 3078, 3021, 1730 (C O), 1635 (C C), 1217,
1165 (SO−3 ) cm−1; 1H NMR (DMSO-d6, 400 MHz)
δ: 3.76 (s, 3H, OCH ), 4.08 (s, 2H, methylene-
3
H), 6.11 (s, 2H), 6.99 (d, 1H, J = 8.4 Hz, ArH),
7.25 (m, 1H, J = 8.4 Hz, ArH), 7.43 (s, 1H), 7.60
(s, 1H); 13C NMR (d6-DMSO, 100 MHz) δ: 32.23,
53.12, 102.41, 109.33, 110.22, 124.54, 127.26, 128.59,
142.17, 148.52, 149.23, 168.26; EI-MS (70 eV) m/z:
251 (M+−SO3Na); Anal. Calcd for C12H11NaO7S2: C
40.68; H 3.13. Found: C 40.43; H 3.20.
General Procedure for Preparation of
Symmetrical Di(Z-allyl) Sulfides 3
In a 25-mL flask Na2S·9H2O (0.13 g, 0.55 mmol), 1
(1 mmol), and anhydrous MeOH (15 mL) were
added. The mixture was stirred at room tempera-
ture for 3–6 h. Upon completion, the reaction mix-
ture was extracted with Et2O (2 × 30 mL), washed
with brine (15 mL), and dried over MgSO4. After
evaporation of the solvent, the residue was purified
by chromatography using cyclohexane: EtOAc (6:1)
as eluent.
Compound 2h. Light yellow solid. mp 103–
104◦C; IR (KBr): 3083−, 3018, 1712 (C O), 1626
1
(C C), 1219, 1159 (SO3 ) cm−1; H NMR (DMSO-
d6, 400 MHz) δ: 3.79 (s, 3H, OCH ), 3.81 (s, 2H,
3
methylene-H), 7.66–7.73 (m, 1H, ArH), 7.78–7.84
(m, 2H), 7.89 (s, 1H), 8.19 (d, 1H, J = 8.0 Hz,
ArH); 13C NMR (d6-DMSO, 100 MHz) δ: 31.50,
53.32, 125.58, 129.66, 130.69, 130.98, 131.79, 135.18,
139.14, 147.67, 167.44; EI-MS (70 eV) m/z: 252
(M+−SO3Na); Anal. Calcd for C11H10NNaO7S2: C
37.18; H 2.84. Found: C 36.90; H 2.91.
Compound 3a. Thick yellow oil. IR (film): 1715
(C O), 1627 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.75 (s, 4H, CH ), 3.84 (s, 6H, OCH ), 7.32–7.40
(m, 6H, ArH), 7.49–7.51 (m, 4H, ArH), 7.76 (s,
2H, ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 30.06,
52.22, 128.57, 128.73, 128.95, 129.62, 134.75, 140.71,
167.73; EI-MS (70 eV) m/z: 382 (M+); Anal. Calcd for
C22H22O4S: C 69.09; H 5.80. Found: C 69.38; H 5.86.
2
3
Compound 2i. Brown solid. mp 109–110◦C; IR
(KBr): 1708 (C O), 1622 (C C), 1284, 1217 (SO−3 )
1
cm−1; H NMR (DMSO-d6, 400 MHz) δ: 3.76 (s, 3H,
Compound 3b. Thick yellow oil. IR (film): 1713
(C O), 1629 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 2.36 (s, 6H, CH ), 3.77 (s, 4H, CH ), 3.83 (s, 6H,
OCH ), 4.17 (s, 2H, methylene-H), 6.73 (dd, 1H,
3
J1 = 4.0 Hz, J2 = 1.6 Hz), 7.30 (d, 1H, J = 4.0 Hz), 7.45
3
2
(s, 1H, ArCH ), 7.93 (d, 1H, J = 1.6 Hz); 13C NMR
OCH ), 7.19 (d, 4H, J = 8.0 Hz, ArH), 7.42 (d, 4H,
3
Heteroatom Chemistry DOI 10.1002/hc

194 Liu et al.
J = 8.0 Hz, ArH), 7.74 (s, 2H, ArCH ); 13C NMR
(CDCl3, 100 MHz) δ: 21.25, 30.03, 52.06, 127.65,
129.26, 129.73, 131.83, 139.15, 141.09, 167.82;
EI-MS (70 eV) m/z: 410 (M+); Anal. Calcd for
C24H26O2S: C 70.22; H 6.38. Found: C 70.56; H 6.35.
2H, J = 8.0 Hz, ArH); 13C NMR (CDCl3, 100 MHz) δ:
30.01, 55.80, 124.94, 129.51, 130.39, 130.74, 131.06,
133.73, 137.73, 147.46, 166.68; EI-MS (70 eV) m/z:
472 (M+); Anal. Calcd for C22H20N2O8S: C 55.93; H
4.27. Found: C 55.58; H 4.32.
Compound 3c. Thick yellow oil. IR (film): 1715
(C O), 1629 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.71 (s, 4H, CH ), 3.85 (s, 6H, OCH ), 7.37 (d, 4H,
Compound 3i. Thick yellow oil. IR (film) 1709
(C O), 1630 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.82 (s, 6H, OCH ), 4.0 (s, 4H, CH ), 6.48 (dd, 2H,
2
3
3
2
J = 8.0 Hz, ArH), 7.44 (d, 4H, J = 8.0 Hz, ArH), 7.69
(s, 2H, ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 29.99,
52.30, 128.86, 129.09, 130.92, 133.08, 135.05, 139.77,
167.41; EI-MS (70 eV) m/z: 450 (M+); Anal. Calcd
for C22H20Cl2O4S: C 58.54; H 4.47. Found: C 58.19,
H 4.54.
J1 = 4.0 Hz, J2 = 1.6 Hz, ArH), 6.72 (d, 2H, J = 4.0
Hz, ArH), 7.46 (s, 2H, ArCH ), 7.54 (d, 2H, J = 1.6
Hz, ArH); 13C NMR (CDCl3, 100 MHz) δ: 29.50,
52.20, 112.20, 116.71, 125.02, 126.72, 144.86, 150.83,
167.88; EI-MS (70 eV) m/z: 362 (M+); Anal. Calcd for
C18H18O6S: C 59.66; H 5.01. Found: C 59.96; H 5.06.
Compound 3d. Thick yellow oil. IR (film): 1719
(C O), 1632 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.56 (s, 4H, CH ), 3.84 (s, 6H, OCH ), 7.29–
7.31 (m, 4H, ArH), 7.38–7.41 (m, 2H, ArH), 7.52–
7.55 (m, 2H, ArH), 7.81 (s, 2H, ArCH ); 13C NMR
(CDCl3, 100 MHz) δ: 30.11, 52.33, 126.83, 129.61,
130.04, 130.44, 130.59, 133.35, 134.17, 137.82,
167.20; EI-MS (70 eV) m/z: 450 (M+); Anal. Calcd
for C22H20Cl2O4S: C 58.54; H 4.47. Found: C 58.21;
H 4.41.
Compound 3j. Thick yellow oil. IR (film): 1718
(C O), 1643 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 2.53 (q, 4H, J = 8.0 Hz, CH ), 2.75 (t, 4H, J = 8.0
2
3
2
Hz, CH ), 3.36 (s, 4H, CH ), 3.72 (s, 6H, OCH ), 6.88
2
2
3
(t, 2H, J = 8.0 Hz, CH ), 7.16–7.29 (m, 10H, ArH);
13C NMR (CDCl3, 100 MHz) δ: 28.07, 29.64, 35.31,
51.90, 126.14, 128.32, 128.41, 129.32, 140.76, 143.91,
167.15; EI-MS (70 eV) m/z: 438 (M+); Anal. Calcd for
C26H30O4S: C 71.20; H 6.89. Found: C 71.58, H 6.81.
Compound 3k. Thick yellow oil. IR (film): 1723
(C O), 1644 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 0.88 (t, 6H, J = 6.8 Hz), 1.27–1.45 (m, 20H), 2.23
(q, 4H, J = 7.5 Hz), 3.49 (s, 4H), 3.76 (s, 6H), 6.85
(t, 2H, J = 7.5 Hz, alkyl-CH ); 13C NMR (CDCl3,
100 MHz) δ: 14.01, 22.56, 28.71, 28.79, 29.04, 29.15,
29.29, 31.68, 51.82, 128.69, 145.43, 167.33; EI-MS
(70 eV) m/z : 426 (M+); Anal. Calcd for C24H42O4S: C
67.56; H 9.92. Found: C 67.90; H 9.82.
Compound 3f. Thick yellow oil. IR (film): 1713
(C O), 1625 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.66 (s, 4H, CH ), 3.79 (s, 6H, OCH ), 3.84 (s,
2
3
6H, OCH ), 6.87 (d, 2H, J = 8.0 Hz, ArH), 6.99
3
(t, 2H, J = 8.0 Hz, ArH), 7.33 (t, 2H, J = 8.0 Hz,
ArH), 7.56 (d, 2H, J = 8.0 Hz, ArH), 7.91 (s, 2H,
ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 30.47, 52.07,
55.34, 110.34, 120.49, 123.89, 128.68, 130.20, 130.45,
136.82, 157.57, 167.79; EI-MS (70 eV) m/z: 442 (M+);
Anal. Calcd for C24H26O6S: C 65.14; H 5.92. Found:
C 65.51; H 5.99.
Compound 3l. Thick yellow oil. IR (film): 1721
(C O), 1643 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 1.07 (t, 6H, J = 7.6 Hz), 2.27 (q, 4H, J = 8.0 Hz),
3.49 (s, 4H), 3.76 (s, 6H), 6.84 (t, 2H, J = 8.0 Hz,
alkyl-CH ); 13C NMR (CDCl3, 100 MHz) δ: 13.24,
22.17, 28.13, 51.89, 128.36, 146.47, 167.41; EI-MS
(70 eV) m/z: 286 (M+); Anal. Calcd for C14H22O4S: C
58.71; H 7.74. Found: C 58.36; H 7.79.
Compound 3g. Thick yellow oil. IR (film); 1711
(C O), 1622 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.74 (s, 4H, CH ), 3.84 (s, 6H, OCH ), 6.01 (s,
2
3
4H, OCH O), 6.74 (s, 2H, ArH), 6.85 (d, 2H, J = 8.0
2
Hz, ArH), 7.06 (d, 2H, J = 8.0 Hz, ArH), 7.67 (s,
2H, ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 30.15,
52.25, 101.41, 108.55, 109.68, 123.38, 125.11, 128.85,
135.50, 141.05, 148.02, 167.95; EI-MS (70 eV) m/z:
470 (M+); Anal. Calcd for C24H22O8S: C 61.27; H 4.71.
Found: C 60.91; H 4.64.
General Procedure for Preparation of
Unsymmetrical Diallysulfides 4
After the sodium (Z)-allyl thiosulfate was readily pre-
pared under an inert atmosphere according to the
procedure mentioned above, allyl bromide (3 mmol)
and In (1.5 mmol) were added to the Bunte salts solu-
tion, the resulting mixture was stirred at room tem-
perature for 30 min. Then, the mixture was stirred
at 55◦C for 8–12 h. Upon completion, the reaction
Compound 3h. Thick yellow oil. IR (film): 1718
(C O), 1636 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 3.41 (s, 4H, CH ), 3.82 (s, 6H, OCH ), 7.51 (d, 2H,
2
3
J = 8.0 Hz, ArH), 7.56 (t, 2H, J = 8.0 Hz, ArH), 7.71
(t, 2H, J = 8.0 Hz, ArH), 7.92 (s, 2H, ArCH ), 8.16 (d,
Heteroatom Chemistry DOI 10.1002/hc

Stereoselective Synthesis of Trisubstituted Alkenes Containing (Z )-Allylthio Units 195
mixture was cooled down to room temperature and
Compound 4e. Thick yellow oil. IR (film): 3075,
extracted by Et2O (2 × 30 mL), washed with brine
(15 mL), and dried over MgSO4. After evaporation of
the solvent, the residue was purified by chromatogra-
phy using cyclohexane:ethyl acetate (6:1) as eluent.
3058, 3023, 1714 (C O), 1632 (C C), 1605 (C C)
1
cm−1; H NMR (CDCl3, 400 MHz) δ: 3.21 (d, 2H,
J = 6.8 Hz), 3.62 (s, 2H), 3.84 (s, 3H), 3.85 (s,
3H), 4.99–5.07 (m, 2H), 5.84 (ddt, 1H, J1 = 16.8 Hz,
J2 = 10.0 Hz, J3 = 6.8 Hz), 6.94 (d, 2H, J = 9.2 Hz,
ArH), 7.50 (d, 2H, J = 9.2 Hz, ArH), 7.71 (s, 1H,
ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 28.17, 35.22,
52.16, 55.31, 113.70, 114.07, 117.15, 127.41, 128.80,
131.63, 134.12, 140.71, 160.26, 168.17; EI-MS (70
eV): m/z (%) 278 (M+); Anal. Calcd for C15H18O3S: C
64.72; H 6.52. Found: C 64.96; H 6.62.
Compound 4a. Thick yellow oil. IR (film): 3081,
3060, 3026, 1716 (C O), 1633 (C C), 1597 (C C)
1
cm−1; H NMR (CDCl3, 400 MHz) δ: 3.16 (d, 2H,
J = 6.8 Hz), 3.59 (s, 2H), 3.86 (s, 3H), 4.84–5.04
(m, 2H), 5.77 (ddt, 1H, J1 = 17.2 Hz, J2 = 10.0 Hz,
J3 = 6.8 Hz), 7.26–7.50 (m, 5H, ArH), 7.76 (s, 1H,
ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 28.11, 36.14,
52.44, 117.33, 125.72, 127.88, 128.82, 129.11, 129.84,
134.34, 140.81, 168.24; EI-MS (70 eV) m/z: 248 (M+);
Anal. Calcd for C14H16O2S: C 67.71; H 6.49. Found:
C 67.50; H 6.62.
Compound 4f. Thick yellow oil. IR (film) 3078,
3060, 3025, 1715 (C O), 1634 (C C), 1598 (C C)
1
cm−1; H NMR (CDCl3, 400 MHz) δ: 3.12 (d, 2H,
J = 6.8 Hz), 3.52 (s, 2H), 3.85 (s, 3H), 3.86 (s,
3H), 4.82–4.96 (m, 2H), 5.73 (ddt, 1H, J1 = 17.2 Hz,
J2 = 10.0 Hz, J3 = 6.8 Hz), 6.90 (d, 1H, J = 7.6 Hz,
ArH), 6.99 (t, 1H, J = 7.6 Hz, ArH), 7.35 (t, 1H,
J = 7.6 Hz, ArH), 7.49 (d, 1H, J = 7.6 Hz, ArH),
7.89 (s, 1H, ArCH ); 13C NMR (CDCl3, 100 MHz)
δ: 28.06, 35.70, 52.10, 55.46, 110.50, 116.88, 120.40,
130.05, 130.23, 130.41, 130.64, 134.22, 136.53,
157.64, 167.88; EI-MS (70 eV) m/z: 278 (M+); Anal.
Calcd for C15H18O3S: C 64.72; H 6.52. Found: C 64.40;
H 6.38.
Compound 4b. Thick yellow oil. IR (film): 3078,
3057, 3023, 1718 (C O), 1631 (C C), 1593 (C C)
cm−1; 1H NMR (CDCl3, 400 MHz) δ: 2.37 (s, 3H,
CH ), 3.17 (d, 2H, J = 7.2 Hz), 3.61 (s, 2H), 3.83
3
(s, 3H), 4.92–5.02 (m, 2H), 5.80 (ddt, 1H, J1 = 16.8
Hz, J2 = 10.0 Hz, J3 = 7.2 Hz), 7.18 (d, 2H, J = 8.0
Hz, ArH), 7.40 (d, 2H, J = 8.0 Hz, ArH), 7.72 (s, 1H,
ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 21.37, 28.01,
35.98, 52.20, 117.14, 125.51, 129.34, 129.76, 132.04,
134.13, 139.21, 140.85, 168.06; EI-MS (70 eV) m/z:
262 (M+); Anal. Calcd for C15H18O2S: C 68.67; H 6.92.
Found: C 68.40; H 6.84.
Compound 4g. Thick yellow oil. IR (film): 3079,
Compound 4c. Thick yellow oil. IR (film): 3076,
3060, 3023, 1714 (C O), 1624 (C C), 1596 (C C)
1
cm−1; H NMR (CDCl3, 400 MHz) δ: 3.21 (d, 2H,
3054, 3023, 1718 (C O), 1632 (C C), 1593 (C C)
1
cm−1; H NMR (CDCl3, 400 MHz) δ: 3.19 (d, 2H,
J = 7.2 Hz), 3.60 (s, 2H), 3.85 (s, 3H), 5.00–5.08 (m,
2H), 5.84 (ddt, 1H, J1 = 16.8 Hz, J2 = 10.0 Hz, J3 = 7.2
Hz), 6.01 (s, 2H), 6.85 (d, 1H, J = 8.4 Hz, ArH), 7.02
(d, 1H, J = 8.4 Hz, ArH), 7.11 (s, 1H, ArH), 7.65 (s,
1H, ArCH ); 13C NMR (CDCl3, 100 MHz) δ: 28.13,
36.08, 52.22, 101.50, 109.65, 117.21, 125.00, 127.36,
128.92, 134.09, 140.68, 148.02, 148.37, 168.02; EI-
MS (70 eV) m/z: 292 (M+); Anal. Calcd for C15H16O4S:
C 61.62; H 5.52. Found: C 61.30; H 5.41.
J = 6.8 Hz), 3.55 (s, 2H), 3.86 (s, 3H), 4.96–5.06
(m, 2H), 5.80 (ddt, 1H,J1 = 17.2 Hz, J2 = 10.0 Hz,
J3 = 6.8 Hz), 7.39 (d, 2H, J = 8.0 Hz, ArH), 7.46 (d,
2H, J = 8.0 Hz, ArH), 7.69 (s, 1H, ArCH ); 13C NMR
(CDCl3, 100 MHz) δ: 27.82, 36.06, 52.35, 117.33,
125.51, 128.86, 129.70, 130.94, 133.29, 133.93,
139.39, 167.66; EI-MS (70 eV) m/z: 282 (35Cl M+),
284 (37Cl M+); Anal. Calcd for C14H15ClO2S: C 59.46;
H 5.35. Found: C 59.21; H 5.43.
Compound 4d. Thick yellow oil. IR (film): 3083,
Compound 4h. Thick yellow oil. IR (film): 3080,
3061, 3020, 1720 (C O), 1636 (C C), 1607 (C C)
cm−1; 1H NMR (CDCl3, 400 MHz) δ 3.09 (d, 2H,
J = 7.6 Hz), 3.35 (s, 2H), 3.88 (s, 3H), 4.80–4.93 (m,
2H), 5.65 (ddt, 1H, J1 = 16.6 Hz, J2 = 10.4 Hz, J3 = 7.6
Hz), 7.54–7.58 (m, 2H, ArH), 7.70 (t, 1H, J = 7.2 Hz,
ArH), 7.96 (s, 1H, ArCH ), 8.18 (d, 1H,J = 7.2 Hz,
ArH); 13C NMR (CDCl3, 100 MHz) δ: 27.71, 35.99,
52.68, 117.34, 125.23, 129.73, 131.33, 131.55, 133.84,
134.19, 137.39, 147.88, 167.22; EI-MS (70 eV) m/z:
293 (M+); Anal. Calcd for C14H15NO4S: C 57.32; H
5.15. Found: C 57.01; H 5.27.
3061, 3025, 1715 (C O), 1634 (C C), 1590 (C C)
1
cm−1; H NMR (CDCl3, 400 MHz) δ: 3.05 (d, 2H,
J = 7.2 Hz), 3.42 (s, 2H), 3.83 (s, 3H), 4.71–4.89
(m, 2H), 5.65 (ddt, 1H, J1 = 16.8 Hz, J2 = 10.0 Hz,
J3 = 7.2 Hz), 7.24–7.31 (m, 2H, ArH), 7.38–7.47 (m,
2H, ArH), 7.77 (s, 1H, ArCH ); 13C NMR (CDCl3, 100
MHz) δ: 27.45, 35.88, 52.35, 117.02, 126.72, 129.62,
129.95, 130.58, 131.30, 133.59, 133.96, 134.20,
137.17, 167.35; EI-MS (70 eV) m/z: 282 (35Cl M+),
284 (37Cl M+); Anal. Calcd for C14H15ClO2S: C 59.46;
H 5.35. Found: C 59.18; H 5.40.
Heteroatom Chemistry DOI 10.1002/hc

196 Liu et al.
Compound 4i. Thick yellow oil. IR (film): 3123,
reaction mixture was quenched with diluted HCl
(5%, 15 mL) and extracted with Et2O (2 × 30 mL),
washed with brine (15 mL), and dried over MgSO4.
After evaporation of the solvent, the residue was pu-
rified by chromatography using cyclohexane:EtOAc
(9:1) (R = alkyl groups) or cyclohexane:EtOAc (6:1)
(R = aryl groups) as eluent.
3081, 1711 (C O), 1632 (C C), 1598 (C C) cm−1;
1H NMR (CDCl3, 400 MHz) δ: 3.21 (d, 2H, J = 6.8
Hz), 3.83 (s, 3H), 3.86 (s, 2H), 5.06–5.11 (m, 2H),
5.85 (ddt, 1H, J1 = 16.8 Hz, J2 = 10.0 Hz, J3 = 6.8
Hz), 6.50 (dd, 1H, J1 = 3.2 Hz, J2 = 1.2 Hz), 6.71 (d,
1H, J = 3.2 Hz), 7.44 (s, 1H, ArCH ), 7.55 (d, 1H,
J = 1.2 Hz); 13C NMR (CDCl3, 100 MHz) δ: 28.07,
35.41, 52.23, 112.52, 116.90, 117.21, 126.00, 126.60,
134.80, 144.99, 151.13, 167.98; EI-MS (70 eV) m/z:
238 (M+); Anal. Calcd for C12H14O3S: C 60.48; H 5.92.
Found: C 60.16; H 5.81.
Compound 5j. Thick yellow oil. IR (film): 1716
(C O), 1643 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 2.62 (q, 4H, J = 8.0 Hz), 2.78 (t, 4H, J = 8.0 Hz),
3.62 (s, 4H), 3.72 (s, 6H), 6.98 (t, 2H, J = 8.0 Hz),
7.19–7.32 (m, 10H); 13C NMR (CDCl3, 100 MHz) δ:
31.32, 35.23, 35.38, 52.29, 126.49, 128.66, 128.77,
128.86, 141.01, 145.43, 167.13; EI-MS (70 eV) m/z:
470 (M+); Anal. Calcd for C26H30O4S2: C 66.35; H
6.42. Found: C 66.72; H 6.48.
Compound 4j. Thick yellow oil. IR (film): 3083,
3062, 1719 (C O), 1638 (C C), 1600 (C C) cm−1; 1H
NMR (CDCl3, 400 MHz) δ: 2.56 (q, 2H, J = 7.6 Hz),
2.77 (t, 2H, J = 7.6 Hz), 3.12 (d, 2H, J = 7.2 Hz),
3.33 (s, 2H), 3.76 (s, 3H), 5.08–5.13 (m, 2H), 5.81
(ddt, 1H,J1 = 17.0 Hz, J2 = 10.0 Hz, J3 = 7.6 Hz), 6.88
Compound 5k. Thick yellow oil. IR (film): 1721
(C O), 1642 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 0.88 (t, 6H, J = 7.2 Hz), 1.25–1.47 (m, 20H), 2.32
(q, 4H, J = 7.2 Hz), 3.70 (s, 4H), 3.77 (s, 6H), 6.95 (t,
2H, J = 7.2 Hz); 13C NMR (CDCl3, 100 MHz) δ: 22.59,
28.84, 29.09, 29.19, 29.24, 29.32, 31.71, 35.29, 51.89,
127.92, 146.78, 166.99; EI-MS (70 eV) m/z: 458 (M+);
Anal. Calcd for C24H42O4S2: C 62.84; H 9.23. Found:
C 62.51; H 9.28.
(t, 1H, J = 7.6 Hz, alkyl-CH ), 7.20–7.32 (m, 5H); 13
C
NMR (CDCl3, 100 MHz) δ: 26.56, 30.74, 34.85, 35.39,
51.96, 117.11, 126.21, 128.35, 128.50, 129.64, 134.39,
140.81, 143.74, 167.32; EI-MS (70 eV) m/z: 276 (M+);
Anal. Calcd for C16H20O2S: C 69.53; H 7.29. Found:
C 69.18; H 7.40.
Compound 4k. Thick yellow oil. IR (film): 3082,
1719 (C O), 1639 (C C), 1601 (C C) cm−1; 1H NMR
(CDCl3, 400 MHz) δ: 0.89 (t, 3H, J = 6.8 Hz), 1.26–
1.50 (m, 10H), 2.23 (q, 2H, J = 7.6 Hz), 3.15 (d, 2H,
J = 6.8 Hz), 3.40 (s, 2H), 3.77 (s, 3H), 5.10–5.20 (m,
2H), 5.85 (ddt, 1H, J1 = 17.2 Hz, J2 = 10.0 Hz, J3 = 6.8
Hz), 6.86 (t, 1H, J = 7.6 Hz, alkyl-CH ); 13C NMR
(CDCl3, 100 MHz) δ: 14.06, 22.61, 26.64, 28.76, 28.90,
29.07, 29.33, 31.73, 35.42, 51.88, 116.99, 127.46,
134.53, 145.29, 167.48; EI-MS (70 eV) m/z: 270 (M+);
Anal. Calcd for C15H26O2S: C 66.62; H 9.69. Found:
C 66.38; H 9.57.
Compound 5l. Thick yellow oil. IR (film): 1719
(C O), 1642 (C C) cm−1; 1H NMR (CDCl3, 400 MHz)
δ: 1.10 (t, 6H, J = 7.2 Hz), 2.30–2.37 (m, 4H), 3.69
(s, 4H), 3.77 (s, 6H), 6.93 (t, 2H, J = 7.2 Hz); 13C
NMR (CDCl3, 100 MHz) δ: 13.34, 22.47, 35.00, 51.85,
127.44, 147.90, 166.97; EI-MS (70 eV) m/z: 318 (M+);
Anal. Calcd for C14H22O4S2: C 52.80; H 6.96. Found:
C 53.23; H 6.90.
Compound 6a [17d]. Thick yellow oil. IR (film):
1709 (C O), 1606 (C C) cm−1; 1H NMR (CDCl3, 400
MHz) δ: 2.19 (s, 3H), 3.89 (s, 3H), 7.37–7.46 (m, 5H),
7.78 (s, 1H); EI-MS (70 eV) m/z: 176 (M+).
General Procedure for the One-Pot Synthesis of
Symmetrical Di(Z-allyl) Disulfides 5 or Methyl
Cinnamic Esters 6
Compound 6b [17d]. Thick yellow oil. IR (film):
1711 (C O), 1632 (C C) cm−1; 1H NMR (CDCl3, 400
MHz) δ: 2.11 (s, 3H), 2.36 (s, 3H), 3.80 (s, 3H), 7.19
(d, 2H, J = 8.0 Hz), 7.31 (d, 2H, J = 8.0 Hz), 7.67 (s,
1H); EI-MS (70 eV) m/z: 190 (M+).
In a 25-mL flask, Na2SSO3·5H2O (0.25 g, 1.0 mmol),
1 (1.0 mmol), and anhydrous MeOH (15 mL) were
added. The mixture was stirred at room temper-
ature for 4–8 h until the sodium (Z)-allyl thio-
sulfates were readily prepared. Methanol was re-
moved and changed solvent into THF (20 mL)
under an inert atmosphere. Then Sm (0.15 g, 1
mmol) and a trace amount of I2 were added to
the resulting mixture followed by dropwise addi-
tion of saturated NH4Cl aqueous solution (4 mL).
The mixture was stirred at room temperature for
the time given in Table 1. Upon completion, the
Compound 6c [17d]. Thick yellow oil. IR (film):
1714 (C O), 1630 (C C) cm−1; 1H NMR (CDCl3, 400
MHz) δ: 2.10 (s, 3H), 3.82 (s, 3H), 7.31 (d, 2H, J = 8.0
Hz), 7.36 (d, 2H, J = 8.0 Hz), 7.62 (s, 1H); EI-MS (70
eV) m/z: 210 (35Cl M+), 212 (37Cl M+).
Compound 6d [17d]. Thick yellow oil. IR (film):
1717 (C O), 1635 (C C) cm−1; 1H NMR (CDCl3, 400
Heteroatom Chemistry DOI 10.1002/hc

Stereoselective Synthesis of Trisubstituted Alkenes Containing (Z )-Allylthio Units 197
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MHz) δ: 2.02 (s, 3H), 3.86 (s, 3H), 7.28–7.47 (m, 4H),
7.78 (s, 1H); EI-MS (70 eV) m/z: (%) 210 (35Cl M+),
212 (37Cl M+).
Compound 6f [17d]. Thick yellow oil. IR (film)
1717 (C O), 1598 (C C) cm−1; 1H NMR (CDCl3, 400
MHz) δ: 2.06 (s, 3H), 3.81 (s, 3H), 3.86 (s, 3H), 6.91–
7.34 (m, 4H), 7.84 (s, 1H); EI-MS (70 eV) m/z: 206
(M+).
Compound 6g [17d]. White solid. mp 75–76◦C;
1
IR (KBr): 1691 (C O), 1600 (C C) cm−1; H NMR
(CDCl3, 400 MHz) δ: 2.11 (s, 3H), 3.81 (s, 3H), 5.99
(s, 2H), 6.82–6.93 (m, 3H), 7.59 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ: 14.2, 52.1, 101.3, 108.4, 109.6,
124.7, 126.6, 129.9, 138.7, 147.6, 147.7, 169.3; EI-MS
(70 eV) m/z: 220 (M+).
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