Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water

Article abstract of DOI:10.1021/acs.joc.6b02459

A newly developed aqueous system with acid and phosphide was introduced in which odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals have high reactivity to react with alkynes, alkenes, and H-phosphine oxides for the synthesis of alkyl and alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably, the chemistry is free of thiol odors, organic solvents, and metals.

Full text of DOI:10.1021/acs.joc.6b02459

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Article
Acid/phosphide-induced radical route to alkyl, alkenyl sulfides
and phosphonothioates from sodium arylsulfinates in water
Ya-mei Lin, Guo-Ping Lu, Gui-Xiang Wang, and Wen-Bin Yi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02459 • Publication Date (Web): 12 Dec 2016
Downloaded from http://pubs.acs.org on December 13, 2016
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Acid/phosphide-induced radical route to alkyl, alkenyl sulfides and
phosphonothioates from sodium arylsulfinates in water
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Yaꢀmei Lin, Guoꢀping Lu,* Guiꢀxiang Wang and Wenꢀbin Yi*
Chemical Engineering College, Nanjing University of Science & Technology Xiaolingwei
200, Nanjing, 210094 (China)
* Eꢀmail: glu@njust.edu.cn, yiwb@njust.edu.cn
Abstract: A newly developed aqueous system with acid and phosphide was introduced in which
odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals
have high reactivity to react with alkynes, alkenes and Hꢀphosphine oxides for the synthesis of
alkyl, alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations
are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably,
the chemistry is free of smell thiols, organic solvents and metals.
Introduction
Thiyl radicals especially arylsulfenyl radicals, which are at the center of some
extremely efficient radical reactions for the synthesis of organosulfur
compounds, have also attracted the interest of synthetic chemists.1 Typically,
arylsulfenyl radicals are generated through three main strategies: (1) the use of
radical initiators; (2) photolysis; (3) thermolysis.2 Nevertheless, most of these
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approaches suffer from limitations including the use of smell, air sensitive
thiols or their derivatives preꢀprepared from them, the demand of metal
catalysts, excess oxidants and toxic organic solvents, and high temperature (in
the cases of thermolysis). Thus, the further exploration of metalꢀfree protocols
for the formation of arylsulfenyl radicals using odorless and easyꢀtoꢀhandle
precursors3 in green solvents under mild conditions is still desirable guided by
the concept of green chemistry and an appealing task in sulfur chemistry.4
Furthermore, the radicals in the ecoꢀfriendly systems may have unique
reactivity compared with thiyl radicals formed via traditional routes, which may
result in new viable accesses to important organosulfur derivatives. On the one
hand, sodium aryl sulfinates are a kind of stable, odorless and easyꢀtoꢀhandle
sulfur compounds that have been widely applied as sulfonating agents2 or
coupling partners via the desulfonation.5 More recently, much attention has
been paid to the construction of CꢀS bonds with these compounds6 and
analogues7 as the sulfur sources under reduction conditions, in which they are
utilized as the precursors of arylsulfide cations. Thus, sodium arylsulfinates
also have great potential to derive the corresponding arylsulfenyl radicals under
designated reduction conditions.
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One the other hand, water is an ideal choice as the reaction medium.8 Our
group has reported a strategy for the in situ generation of arylsulfenyl radicals
from sodium arylsulfinates in aqueous reduction systems using I2 and PPh3 to
achieve the iodothiolation of alkynes.9 Along this line, we develop a new
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aqueous system (acid/phosphide) for the synthesis of alkyl, alkenyl sulfides and
phosphonothioates under relatively mild conditions, in which arylsulfenyl
radicals can be derived from sodium arylsulfinates. To the best of our
knowledge, there is the first example on the formation of arylsulfenyl radicals
under acidic and reductive conditions. Furthermore, the generation mechanism
of arylthiyl radicals in the system is also investigated by performing the control
experiments and quantum chemical calculations.
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Results and discussion
During the investigations of the synthesis of β
ꢀiodoalkenyl sulfides,9 trace of
alkenyl sulfide 3a was found in the presence of base (Table 1, entry 1).
Encouraged by these results, we further optimized the reaction conditions. The
results indicate that I2 is not necessary for the reaction and the use of strong
acid (H2SO4) in place of base can afford the best yield in the model reaction
(entries 2ꢀ8). Both acid and reducer are necessary for the reaction (entry 9, 15).
The amounts of H2SO4, sodium pꢀtoluenesulfinate and reaction temperature
were also optimized (entries 10ꢀ18). The best option was using 2.0 equiv of
ꢀtoluenesulfinate and 0.5 equiv of H2SO4 in 80 oC (entry 15).
sodium
Potassium
15), but sodium
p
p
ꢀtoluenesulfinate could also provide a satisfactory yield (entry
pꢀtoluenesulfinate is cheaper. Various reducing agents such as
hydrazine hydrate, Zn powder, HCOOH, iodotrimethylsilane (TMSI) and dietyl
phosphite were also screened (entries 19ꢀ23). Only phosphide could afford the
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desired product, and PPh3 emerged as the best choice. The desired product 3a
was also afforded with moderate yield (55%) in the case of toluenesulfinic acid
even without H2SO4, indicating that acid may be used to form toluenesulfinic
acid in situ and promote the reaction (entry 24).
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Table 1. The optimization of reaction conditionsa
entry
1
2
3
4
5
6
7
additive (x equiv)
NaOH/I2 (1.2/1.5)
NaOH (1.2)
TsOH (1.2)
HOCH2COOH (1.2)
AcOH (1.2)
CF3COOH (1.2)
HCl (1.2)
reducer
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
t (oC)
120
120
120
120
120
120
120
120
120
120
80
80
50
25
80
80
80
80
80
yield (%)b
Z/Eb
91/9
/
82/18
83/17
64/36
77/23
56/44
14/86
/
19/81
17/83
32/68
66/34
77/23
17/83
16/84
17/83
17/83
16/84
/
25
trace
33
42
54
31
68
86
nr
8
9
H2SO4 (1.2)
/
PPh3
PPh3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
H2SO4 (1.5)
H2SO4 (1.5)
H2SO4 (1.5)
H2SO4 (1.5)
H2SO4 (1.5)
H2SO4 (0.5)
H2SO4 (0.3)
H2SO4 (1.0)
H2SO4 (2.0)
H2SO4 (0.5)
H2SO4 (0.5)
H2SO4 (0.5)
H2SO4 (0.5)
H2SO4 (0.5)
/
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
94
98
88c
90
44
96, 94d, nre
84
95
99
69
nr
nr
nr
PPh3
(EtO)2P(O)H
.
N2H4 H2O
80
80
80
80
Zn
HCOOH
TMSI
PPh3
/
/
/
nr
80
55f
13/87
a
Reaction conditions: 4ꢀchlorophenylacetylene 0.250 mmol, sodium pꢀtoluenesulfinate 0.500
mmol, PPh3 0.750 mmol, additive x equiv, H2O 1.0 mL, t oC, 10 h. b The yield of 3a and Z/E ratio
were determined by GCꢀMS and 1H NMR on crude products.
1.5 equiv of sodium
c
pꢀtoluenesulfinate was used. d 2 equiv of potassium pꢀtoluenesulfinate was used. e Without PPh3. f
2 equiv of toluenesulfinic acid instead of sodium pꢀtoluenesulfinate was used.
With the optimized conditions in hands, the scope of the reaction was studied
(Table 2). Generally, Eꢀisomer adducts were the main products because they are
the thermodynamic products, and the stereoselectivity was more than 80%. A
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range of terminal arylethynes containing electronꢀdonating and ꢀwithdrawing
5
6
7
groups reacted with
1 to give the corresponding adducts in moderate to
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9
excellent yields (entries 1ꢀ7, 15ꢀ20). Aliphatic alkynes could also provide the
corresponding products but the stereoselectivity was poor (entries 8ꢀ11).
Heteroaryl acetylenes were also applied in the reaction successfully with
satisfactory results (entries 12ꢀ14).
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Table 2. The hydrothiolation of alkynes with sodium arylsulfinatesa
H2SO4, PPh3
S
Ar SO2Na
+
R
R
Ar
H2O, 80 o
C
1
2
3
entry
1
2
3
4
5
6
7
8
Ar
R
yield (%)b
74d
92
E/Zc
3
Eꢀ3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
Eꢀ3l
Eꢀ3m
3n
3o
3p
3q
3r
4ꢀCH3C6H4
4ꢀClC6H4
83/17
86/14
85/15
85/15
88/12
80/20
87/13
53/47
46/54
60/40
64/36
81/19
99/1
15/85
88/12
90/10
90/10
82/18
50/50
89/11
4ꢀCH3C6H4 4ꢀCH3C6H4
4ꢀCH3C6H4 4ꢀMeOC6H4
4ꢀCH3C6H4 4ꢀnꢀBuC6H4
4ꢀCH3C6H4
4ꢀMeOC6H4
4ꢀMeOC6H4 4ꢀCF3C6H4
4ꢀCH3C6H4
4ꢀCH3C6H4
4ꢀMeOC6H4 cyclopentyl
4ꢀMeOC6H4 cyclohexyl
4ꢀMeOC6H4
4ꢀMeOC6H4
4ꢀClC6H4
Ph
83
90
89
89
96
79
78
90
4ꢀBrC6H4
4ꢀClC6H4
nꢀC4H9
nꢀC8H17
9
10
11
12
13
14
15
16
17
18
19
20
92
2ꢀpyridyl
3ꢀpyridyl
2ꢀthienyl
Ph
72d
90d
89
72
92
90
96
82
91
Mesityl
Ph
Ph
Ph
Ph
2ꢀCH3C6H4
4ꢀClC6H4
2ꢀBrC6H4
4ꢀMeOC6H4
3s
3t
Ph
a
Reaction conditions: sodium arenesulfinate 1 0.500 mmol, alkynes 2 0.250 mmol, PPh3 0.750
mmol, H2SO4 0.125 mmol, H2O 1.0 mL, 80 C, 10 h. b Isolated yields, a mixture of E and Z
stereoisomers. c E/Z ratio was determined by GCꢀMS and H NMR on crude products. The
o
1
d
isolated yields of E isomers.
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Table 3. The optimization of reaction conditionsa
Acid
PPh3
H2O
S
SO2Na
+
Cl
Cl
1a
4a
entry
x
tempreture (oC) yield (%)b
1
2
3
4
5
6
7
8
1.5
1.5
1.5
1.5
1.5
/
130
100
80
50
25
50
50
50
87
63
68
34
14
8
9
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nr
2.0
3.0
70
91 (87)c
a Reaction conditions: 4ꢀchlorostyrene 0.250 mmol, sodium pꢀtoluenesulfinate 0.375 mmol, PPh3
0.750 mmol, acid x equiv, H2O 1.0 mL, t oC, 10 h. b GC yields. c Isolated yield.
Likewise, the approach was also applied in the hydrothiolation of alkenes by
o
just increasing the amount of acid to 3.0 equiv at 50 C (Table 3). Further
investigations indicated that sodium arylsulfinates could react with a series of
arylalkenes to yield the final products (Scheme 1, 4a
ꢀ4f, 4m, 4n), and
alkylalkenes can also provide the desire adducts (4h 4l). Nevertheless, most
ꢀ
electronꢀdeficient alkenes failed to be employed in the reaction (such as
4ꢀnitrostyrene and chalcone), and only 52% yield of 4g was produced using
N
ꢀbenzylꢀ1Hꢀpyrroleꢀ2,5ꢀdione. The product 4o was afforded from
trimethylvinylsilane via addition and substitution reactions. The results of
control experiments indicate that H2SO4 can enhance the reduction of sodium
arylsulfinates (Scheme 1, eq. 1), and the hydrogen source is mainly from water
(eq. 2). In addition, PPh3 could not reduce PhS(O)CH2CH2Ph or
PhS(O2)CH2CH2Ph to sulfur product PhSCH2CH2Ph (eq. 3).
It should be noted that phosphonothioates which have promising bioactivities
and pestꢀcontrol applications,10 could also be generated using
Hꢀphosphine
oxides instead of PPh3 as the reducing agent at room temperature. Compared
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with other approaches for the synthesis of these compounds,11 the protocol is
free of metal catalysts and organic solvents and no heating is required. The acid
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9
(H2SO4) proved to be necessary for the reaction. Reactions of
oxides occurred in moderate to good yields (Scheme 2, 5a 5b
formation of products was also observed in the cases of diaryl
chlorophosphines without acid (5a 5c 5e). A solvent switch to DMF along
H
ꢀphosphine
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,
,
5f 5h). The
ꢀ
,
ꢀ
with an increase in reaction temperature to 100 °C was found to improve the
poor yields of 5i and 5j. A poor yield of 5k was obtained using sodium
methanesulfinate instead of sodium arylsulfinates.
Scheme 1. The hydrothiolations of alkenes with sodium arylsulfinatesa
O
S
R
R1
S
Ph
N
Ph
S
R1 = 4-ClC6H4 4a, 87%
R1 = 4-MeC6H4 4b, 90%
R1 = 4-BrC6H4 4c, 80%
4d
Ph
O
4e
R = Cl 79%,
R = Me 83%, 4f
52%, 4g
R1 = mesityl
, 96%
R1 = 2-pyridyl
4m
, 95%
Br
S
S
C6H13
Ar'
S
Cl
4h
Ar' = 4-MeOC6H4
Ar' = Ph
, 76%
4j, 96%
4k, 98%
4i, 97%
OMe
S
S
S
S
S
4l
4n
4o
, 80%
, 98%
, 83%
PPh3 (3 equiv)
S
Ar
S
Ar SO2Na
Ar SH
+
Ar
H2O, rt, 10 h
(1)
H2SO4 3 equiv
H2SO4 0 equiv
68%
0%
30%
0%
Ar = p-tolyl
Ar SO2Na, 1.5 equiv
H2SO4, 3 equiv
D
S
Ar (2)
PPh3, 3 equiv
Cl
H2O, 50 oC, 10 h
4a-D
Cl
Ar = p-tolyl
4a-D:4a = 75:25b
D2O instead of H2O
SO2Ph
H2SO4 PPh3
H2O, 50 oC, 10 h
Ph
O
S
S
(3)
Ph
Ph
Ph
Ph
a Reaction conditions: sodium arenesulfinate 0.375 mmol, alkene 0.250 mmol, PPh3 0.750 mmol,
H2SO4 0.750 mmol, H2O 1.0 mL, 50 oC, 10 h. Isolated yields. b Based on 1H NMR results.
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To further probe the mechanism, radical trapping experiments were designed
and investigated (see Table S1, SI). All the reactions were inhibited in the
presence of radical traps (TEMPO, BHT, 1,1ꢀdiphenylethylene). All three
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radical trapping products (
A
ꢀ
C
) were observed by GCꢀMS, and A, C were
separated and further identified by H and 13C NMR suggesting these
transformations may include radical processes. The further electron
paramagnetic resonance (EPR) experiments also indicate that free radicals are
generated in H2SO4/PPh3 system (Figure S1, SI).
1
Scheme 2. The reactions of sodium arylsulfinates and H-phosphine oxidesa
O
P
O
P
O
S
OEt MeO
S
OPh
S
P
Ph
OEt
5i, 12%, 71%c
OPh
5j, 15%, 78%c
Ph
5k, 30%d
a
Conditions: sodium arylsulfinates 0.250 mmol, Hꢀphosphine oxides 0.500 mmol, H2SO4 0.125
b
mmol, H2O 1.0 mL, rt, 6 h. Isolated yields. Use of diaryl phosphate chloride instead of
c
Hꢀphosphine oxides in the absence of H2SO4. The reaction was performed in DMF without
H2SO4 at 100 oC for 6 h. d Sodium methanesulfinate was used in place of sodium arylsulfinate.
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Table 4. The calculated values of some possible intermediates’ BDEs based on quantum
calculations
6
7
8
9
BDE (kJ/mol)
Compounds Dissociation bond
B3LYP/6ꢀ31G* B3LYP/6ꢀ311G*
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SꢀS
SꢀS
O=SꢀO
SꢀO
SꢀS
SꢀS
165.25
1.75
37.14
134.29
119.49
167.12
4.33
32.76
133.09
121.43
228.14
190.09
7a
8a
9a
10a
11a
Br2
230.40
BrꢀBr
221.94 (192)a
a Actual measured value.
Control experiments were also performed to confirm whether
Sꢀphenyl
benzene sulfonothioate, 1,2ꢀdiꢀ ꢀtolyl disulfane or 4ꢀmethylbenzenethiol were
p
the intermediates in the system (Table S2, SI). Although the desired products
could be obtained with satisfactory yields in some cases, these reactions did not
contain a radical route. Thus, all of them prove to be not the intermediates in
these reactions. According to the calculation results of the bond dissociation
energies (BDEs) (Table 4), it can be concluded that 8a, 10a have more
probability to yield radical by homolysis than other intermediates.12
Based on these results, a proposed mechanism of the formation of aryl
sulfenyl radicals in H2SO4/PPh3 system was illustrated in Figure 1.
8 and 10
that are generated from sodium arylsulfinates in H2SO4/PPh3 system,12a can
form arylthiyl radicals 13 and arylsulfinyl radicals 12 (paths
I and II) by
homolysis. Radicals 12 can further yield radicals 13 through reduction or
disproportionation (paths III or IV). Relative free energy profiles for paths I-IV
(Figure 2) were also provided based on the studies of density functional theory
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(DFT) (see Table S3, SI). The free energy barriers of path
I and II are close,
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9
while the free energy barrier of path III is much lower than path IV. Thus,
to III or path II to III 13
radicals 13 are more likely to be afforded from path
I
.
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Further control experiments indicated that 10a can be observed in the reaction
of phenylsulfanol itself while 7a instead of 8a was detected in the reaction of
phenylsulfanol with benezenesulfinic acid.12,14 These results also supported the
proposed mechanism in Figure 1.
H+
H+
Ar SO2H
Ar SO2Na
Ar
S OH
PPh3
H
path I
O
S
H
S
O
S
Ar
S
+
OH
O
S
O
O
Ar
Ar
2
Ar
Ar
S
Ar
Ar
Ar SO2H
8
O
Ar
H
path II
H
S
O
O
S
Ar
Ar
S
+
S
OH
OH
Ar
S O
O
S
+
Ar
S
Ar
S
Ar
10
PPh3
path III
path IV
Ar
Ar
S
O
O
PPh3
O
PPh3
O
O
S
Ar
Ar
S
13
S
O
Ar
Ar
12
S
S Ar
O2S
Figure 1. The proposed mechanism of the sulfenyl radical generation from sodium
arylsulfinates in H2SO4/PPh3 system.
Figure 2. Relative free energy profiles (kJ/mol) for paths IꢀIV.
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Figure 3. Tentative mechanisms.
Although the detailed mechanisms of these reactions remained to be
elucidated, a tentative pathway for the hydrothiolations of alkenes was
proposed (Figure 3). Arylsulfenyl radical in situ generated form sodium
arylsulfinite based on the processes in Figure 2, adds to alkene to afford carbon
radical intermediate, following hydrogen atom transfer (HAT) process with aryl
thiol to form the final product.15 The mechanism of the formation of SꢀP bonds
was also proposed (Figure 3). There are two pathways for the transformation.
The reaction can be inhibited by TEMPO, in which the radical trapping product
is separated and further identified by 1H, 13C NMR and GCꢀMS (Table S1, SI),
so the radical process may be the major path (path B) of the reaction.
Conclusions
In conclusion, we have reported a stable and odorless arylsulfenyl radical
precursor, sodium arylsulfinate, which can be applied to several
transformations for the construction of organosulfur compounds in
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H2SO4/phosphide aqueous system. The radical trap experiments and EPR
results indicate that these transformations contain radical processes. The
formation mechanism of arylthiyl radicals in the system is also investigated by
performing the control experiments and quantum chemical calculations. Acid
promote the reduction of sodium arenesulfonates and the phosphide as a
reducing agent may be enhance the generation of arylsulfenyl radicals.
Although low atom economy and potential water pollution exist in the
chemistry, it is free of thiols, organic solvents and metal catalysts, and provides
a new application of sodium arylsulfinates in organic synthesis, which may
promote the discovery of other new types of radical sulfuration reactions for the
construction of sulfurꢀcontaining compounds.
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Experimental Section
General procedures for the synthesis of alkenyl sulfides 3: A mixture of sodium
arylsulfinate
1 0.500 mmol, alkyne 2 0.250 mmol, PPh3 0.750 mmol and 0.125 mmol
o
H2SO4 in water (1.0 mL) was stirred at 80 C for 10 h. Upon completion, the reaction
mixture was diluted with EtOAc (4.0 mL), filtered through a bed of silica gel layered over
Celite. The volatiles were removed in vacuo to afford the crude product. Further column
chromatography on silica gel (EtOAc/petroleum ether, v/v = 1/20) was needed to afford the
pure desired products
3. In the cases of Eꢀ3l and Eꢀ3m, the eluent composition is 1/10
(EtOAc/petroleum ether, v/v).
General procedures for the synthesis of alkyl sulfides 4: A mixture of sodium
arylsulfinate
1 0.375 mmol, alkene 0.250 mmol, PPh3 0.750 mmol and 0.75 mmol H2SO4
in water (1.0 mL) was stirred at 50 oC for 10 h. Upon completion, the reaction mixture was
diluted with EtOAc (4.0 mL), filtered through a bed of silica gel layered over Celite. The
volatiles were removed in vacuo to afford the crude product. Further column
chromatography on silica gel (EtOAc/petroleum ether, v/v = 1/20) was needed to afford the
pure desired products
ether, v/v).
4. In the case of 4g, the eluent composition is 1/5 (EtOAc/petroleum
General procedures for the synthesis of phosphonothioates 5: A mixture of sodium
arylsulfinate 0.250 mmol, ꢀphosphine oxide 0.500 mmol and H2SO4 0.125 mmol in
1
H
water (1.0 mL) was stirred at room temperature for 6 h. Upon completion, the reaction
mixture was diluted with EtOAc (4.0 mL), filtered through a bed of silica gel layered over
Celite. The volatiles were removed in vacuo to afford the crude product. Further column
chromatography on silica gel (EtOAc/petroleum ether, v/v = 1/4) was needed to afford the
pure desired products 5.
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Characterization data of all products
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(E)ꢀ(4ꢀChlorostyryl)(pꢀtolyl)sulfane.16 Eꢀ3a, yellow oil (74%, 48.1 mg). H NMR (CDCl3, 500
MHz) δ 2.36 (s, 3H), 6.54 (d, J = 15.5 Hz, 1H), 6.84 (d, J = 15.5 Hz, 1H), 7.17 (d, J = 8.0 Hz, 2H),
7.22 (d, J = 9.0 Hz, 2H), 7.23ꢀ7.27 (m, 2H), 7.33 (d, J = 8.0 Hz, 2H). 13C NMR (CDCl3, 125 MHz)
δ 20.1, 124.7, 126.0, 127.5, 127.8, 129.0, 129.6, 130.0, 131.9, 134.2, 136.6. GCꢀMS (EI) m/z: 260.
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(4ꢀMethylstyryl)(pꢀtolyl)sulfane.17,18 3b, yellow oil, was obtained as a mixture of stereoisomers in
86:14 (E/Z) ratio (92%, 55.2 mg). 1H NMR (500 MHz, CDCl3) δ 2.26 (s, 3H, Zꢀ3b ), 2.27 (s, 3H,
Eꢀ3b), 2.29 (s, 3H, Eꢀ3b), 2.31 (s, 3H, Zꢀ3b), 8.34 (d, J = 10.5 Hz, 1H, Zꢀ3b), 8.47 (d, J = 10.5 Hz,
1H, Zꢀ3b), 6.60 (d, J = 15.5 Hz, 1H, Eꢀ3b), 6.74 (d, J = 15.5 Hz, 1H, Eꢀ3b), 7.05 (d, J = 8.0 Hz,
2H (Eꢀ3b)), 7.09 (d, J = 8.0 Hz, 2H (Eꢀ3b), 2H (Zꢀ3b)), 7.14 (d, J = 8.5 Hz, 2H (Zꢀ3b)), 7.16 (d, J
= 8.0 Hz, 2H (Eꢀ3b)), 7.26 (d, J = 8.0 Hz, 2H (Eꢀ3b)), 7.30 (d, J = 8.0 Hz, 2H (Zꢀ3b)), 7.37 (d, J =
8.0 Hz, 2H (Zꢀ3b)). 13C NMR (125 MHz, CDCl3) δ 21.2, 21.3, 123.1, 126.0, 126.8 (Z), 128.8,
129.1, 129.5, 130.1, 130.5, 131.2, 131.7 (Z), 134.1 (Z), 137.2, 137.5. GCꢀMS (EI) m/z: 240.
(4ꢀMethoxystyryl)(pꢀtolyl)sulfane.17,18 3c, yellow oil, was obtained as a mixture of stereoisomers
in 85:15 (E/Z) ratio (83%, 59.5 mg). 1H NMR (500 MHz, CDCl3) δ 2.37 (s, 3H (Zꢀ3c), 3H (Eꢀ3c) ),
3.83 (s, 3H, Eꢀ3c), 3.85 (s, 3H, Zꢀ3c), 6.37 (d, J = 11.0 Hz, 1H (Zꢀ3c)), 6.54 (d, J = 10.5 Hz, 1H
(Zꢀ3c)), 6.70 (d, J = 15.5 Hz, 1H (Eꢀ3c)), 6.74 (d, J = 15.5 Hz, 1H (Eꢀ3c)), 6.88 (d, J = 8.5 Hz, 2H
(Eꢀ3c)), 6.96 (d, J = 8.5 Hz, 2H (Zꢀ3c)), 7.17 (d, J = 8.0 Hz, 2H (Eꢀ3c), 2H (Zꢀ3c)), 7.30 (d, J =
8.5 Hz, 2H (Eꢀ3c)), 7.34 (d, J = 8.0 Hz, 2H (Eꢀ3c)), 7.39 (d, J = 8.0 Hz, 2H (Zꢀ3c)), 7.52 (d, J =
9.0 Hz, 2H (Zꢀ3c)). 13C NMR (125 MHz, CDCl3) δ 21.2, 55.5, 113.9 (Z), 114.3, 121.4, 124.4 (Z),
126.6 (Z), 127.4, 129.7 (Z), 130.1, 130.2, 130.5, 131.5, 132.0, 137.0, 159.4. GCꢀMS (EI) m/z: 256.
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(4ꢀButylstyryl)(pꢀtolyl)sulfane. 3d, yellow oil, was obtained as a mixture of stereoisomers in
85:15 (E/Z) ratio (90%, 63.5 mg). H NMR (500 MHz, CDCl3) δ 0.88 (t, J = 8.0 Hz, 3H (Eꢀ3d),
1
3H (Zꢀ3d)), 1.27ꢀ1.35 (m, 2H (Eꢀ3d), 2H (Zꢀ3d)), 1.49ꢀ1.60 (m, 2H (Eꢀ3d), 2H (Zꢀ3d)), 2.30 (s,
3H (Eꢀ3d), 3H (Zꢀ3d)), 2.54 (t, J = 8.0 Hz, 2H (Eꢀ3d), 2H (Zꢀ3d)), 6.35 (d, J = 10.5 Hz, 1H
(Zꢀ3d)), 6.48 (d, J = 11.0 Hz, 1H (Zꢀ3d)), 6.63 (d, J = 15.5 Hz, 1H (Eꢀ3d)), 6.76 (d, J = 15.5 Hz,
1H (Eꢀ3d)), 7.07 (d, J = 8.0 Hz, 2H (Eꢀ3d)), 7.10 (d, J = 8.0 Hz, 2H (Eꢀ3d), 2H (Zꢀ3d)), 7.16 (d, J
= 7.5 Hz, 2H (Zꢀ3d)), 7.20 (d, J = 7.5 Hz, 2H (Eꢀ3d)), 7.27 (d, J = 8.0 Hz, 2H (Eꢀ3d)), 7.31 (d, J =
8.0 Hz, 2H (Zꢀ3d)), 7.40 (d, J = 8.0 Hz, 2H (Zꢀ3d)), 13C NMR (125 MHz, CDCl3) δ 14.1, 21.1,
22.5, 33.7, 35.5, 123.1, 126.1, 126.8 (Z), 128.5 (Z), 128.9, 130.1, 130.4, 130.6 (Z), 131.4, 131.8,
134.3, 137.2, 142.6. HRMS (EI) Calcd. for C19H22S 282.1442, found 282.1443.
(4ꢀBromostyryl)(pꢀtolyl)sulfane.19 3e, yellow oil, was obtained as a mixture of stereoisomers in
88:12 (E/Z) ratio (89%, 67.6 mg). H NMR (500 MHz, CDCl3) δ 2.25 (s, 3H, Zꢀ3e), 2.29 (s, 3H,
Eꢀ3e), 6.38 (d, J = 11.0 Hz, 1H (Zꢀ3e)), 6.42ꢀ6.47 (m, 1H (Zꢀ3e), 1H (Eꢀ3e)), 6.79 (d, J = 15.5 Hz,
1H (Eꢀ3e)), 7.03 (d, J = 8.0Hz, 2H (Zꢀ3e)), 7.09ꢀ7.11 (m, 4H (Eꢀ3e), 2H (Zꢀ3e)), 7.26ꢀ7.31 (m, 2H
(Eꢀ3e), 2H (Zꢀ3e)), 7.34 (d, J = 8.5 Hz, 2H (Eꢀ3e)), 7.43 (d, J = 8.5 Hz, 2H (Zꢀ3e)). 13C NMR (125
MHz, CDCl3) δ 21.2, 121.1, 125.3 (Z), 126.1, 127.5, 128.4 (Z), 128.5, 128.7 (Z), 130.0 (Z), 130.2
130.4 (Z), 130.7 (Z), 130.8 (Z), 131.2, 131.5, 131.9, 135.8, 137.8. GCꢀMS (EI) m/z: 304.
1
(4ꢀchlorostyryl)(4ꢀmethoxyphenyl)sulfane.20 3f, yellow oil, was obtained as a mixture of
stereoisomers in 80:20 (E/Z) ratio (89%, 61.4 mg). H NMR (500 MHz, CDCl3) δ 3.75 (s, 3H,
1
Zꢀ3f), 3.76 (s, 3H, Eꢀ3f), 6.32ꢀ6.35 (d, J = 16.0Hz, 1H (Eꢀ3f)), 6.32ꢀ6.35 (m, 2H, Zꢀ3f), 6.73ꢀ6.76
(d, J = 15.5Hz, 1H (Eꢀ3f)), 6.82ꢀ6.86 (m, 2H (Eꢀ3f), 2H (Zꢀ3f)), 7.11ꢀ7.13 (d, J = 8.5Hz, 2H
(Eꢀ3f)), 7.16ꢀ7.19 (m, 2H, Eꢀ3f), 7.27ꢀ7.29 (d, J = 8.5Hz, 2H (Zꢀ3f)), 7.33ꢀ7.36 (m, 2H (Eꢀ3f), 2H
(Zꢀ3f)), 7.37ꢀ7.39 (m, 2H, Zꢀ3f). 13C NMR (125 MHz, CDCl3) δ 55.5, 115.1, 124.1, 124.6(Z),
127.1, 127.2, 128.6, 128.9, 129.4(Z), 130.0(Z), 132.8, 133.2(Z), 134.0, 135.4, 160.0. GCꢀMS (EI)
m/z: 276.
(4ꢀMethoxyphenyl)(4ꢀ(trifluoromethyl)styryl)sulfane. 3g, white solid, m.p. 72ꢀ74 oC, was obtained
as a mixture of stereoisomers in 87:13 (E/Z) ratio (96%, 74.4 mg). 1H NMR (500 MHz, CDCl3) δ
3.75 (s, 3H, Zꢀ3g), 3.76 (s, 3H, Eꢀ3g), 8.33 (d, J = 15.5Hz, 1H (Eꢀ3g)), 8.40 (d, J = 11.0 Hz, 1H
(Zꢀ3g)), 8.47 (d, J = 11.0 Hz, 1H (Zꢀ3g)), 6.82ꢀ6.90 (m, 3H (Eꢀ3g), 2H (Zꢀ3g)), 7.26 (d, J = 8.0Hz,
2H (Eꢀ3g)), 7.35 (d, J = 8.0 Hz, 2H (Eꢀ3g), 2H (Zꢀ3g)), 7.44 (d, J = 8.5 Hz, 2H (Eꢀ3g)), 7.53 (d, J
= 8.5 Hz, 2H (Zꢀ3g)), 7.55 (d, J = 8.5 Hz, 2H (Zꢀ3g)). 13C NMR (125 MHz, CDCl3) δ 54.4, 113.9
(Z), 114.1, 123.2 (q, J = 275.0 Hz, 1C), 122.2 (Z), 123.0 (Z), 124.6, 124.7, 124.9, 127.6 (q, J =
31.3 Hz, 1C), 127.7, 128.8, 130.8 (Z), 132.2 (Z), 133.3, 139.2, 160.0. HRMS (EI) Calcd. for
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C16H13F3OS 310.0639, found 310.0634.
Hexꢀ1ꢀenꢀ1ꢀyl(pꢀtolyl)sulfane.21 3h, yellow oil, was obtained as a mixture of stereoisomers in
53:47 (E/Z) ratio (79%, 40.7 mg). H NMR (500 MHz, CDCl3) δ 0.91ꢀ0.96 (m, 3H (Zꢀ3h), 3H
(Eꢀ3h) ), 1.33ꢀ1.46 (m, 3h (Zꢀ3h), 3h (Eꢀ3h) ), 2.14ꢀ2.34 (m, 5H (Zꢀ3h), 5H (Eꢀ3h) ), 5.76ꢀ5.78 (m,
1H, Zꢀ3h), 5.92ꢀ5.95 (m, 1H, Zꢀ3h), 6.10ꢀ6.18 (m, 2H, Eꢀ3h), 7.12 (d, J = 8.0 Hz, 2H (Eꢀ3h), 2H
(Zꢀ3h)), 7.23ꢀ7.27 (m, 2H (Eꢀ3h), 2H (Zꢀ3h) ). 13C NMR (125 MHz, CDCl3) δ 14.0, 21.1, 22.3,
22.4 (Z), 28.9 (Z), 31.3, 32.9, 121.7 (Z), 123.7, 129.3 (Z, 2C), 129.4 (2C), 129.8 (4C), 132.7 (Z),
136.4. GCꢀMS (EI) m/z: 206.
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Decꢀ1ꢀenꢀ1ꢀyl(pꢀtolyl)sulfane. 3i, yellow oil, was obtained as a mixture of stereoisomers in 46:54
(E/Z) ratio (78%, 51.1 mg). H NMR (CDCl3, 500 MHz) δ 0.82ꢀ0.84 (m, 3H (Zꢀ3i), 3H (Eꢀ3i)),
1
1.23ꢀ1.28 (m, 10H (Zꢀ3i), 10H (Eꢀ3i)), 1.34ꢀ1.39 (m, 2H (Zꢀ3i), 2H (Eꢀ3i)), 2.06ꢀ2.10 (m, 1H
(Zꢀ3i), 1H (Eꢀ3i)), 2.16ꢀ2.20 (m, 1H (Zꢀ3i), 1H (Eꢀ3i)), 2.26 (m, 3H (Zꢀ3i), 3H (Eꢀ3i)), 5.68ꢀ5.73
(m, 1H, Eꢀ3i), 5.84ꢀ5.89 (m, 1H, Zꢀ3i), 6.03ꢀ6.10 (m, 1H (Zꢀ3i), 1H (Eꢀ3i)), 7.04ꢀ7.06 (m, 2H
(Zꢀ3i), 2H (Eꢀ3i)), 7.16ꢀ7.20 (m, 2H (Zꢀ3i), 2H (Eꢀ3i)). 13C NMR (CDCl3, 125 MHz) δ 14.2, 21.1,
22.8, 29.2 (2C), 29.4, 29.5, 32.0, 33.2, 121.7, 123.6, 129.4 (E), 129.8 (2C (Zꢀ3i), 2C (Eꢀ3i)), 132.8,
136.3 (E), 136.5. HRMS (EI) Calcd. for C17H26S 262.1755, found 262.1750.
(2ꢀCyclopentylvinyl)(4ꢀmethoxyphenyl)sulfane. 3j, yellow oil, was obtained as a mixture of
1
stereoisomers in 60:40 (E/Z) ratio (90%, 52.7mg). H NMR (500 MHz, CDCl3) δ 1.19ꢀ1.27 (m,
2H (Eꢀ3j), 2H (Zꢀ3j)), 1.48ꢀ2.59 (m, 7H (Eꢀ3j), 7H (Zꢀ3j)), 3.73 (s, 3H (Eꢀ3j), 3H (Zꢀ3j)),
5.58ꢀ5.59 (m, 1H, Zꢀ3j), 5.72ꢀ5.76 (m, 1H, Eꢀ3j), 5.95ꢀ6.00 (m, 1H (Eꢀ3j), 1H (Zꢀ3j)), 6.77ꢀ6.80
(m, 2H (Eꢀ3j), 2H (Zꢀ3j)), 7.22ꢀ7.26 (m, 2H (Eꢀ3j), 2H (Zꢀ3j)). 13C NMR (125 MHz, CDCl3) δ
25.2, 25.5, 33.1, 33.3, 40.2 (Z), 43.8, 55.5, 114.8, 121.2, 123.5(Z), 125.9(Z), 126.5(Z), 127.1(Z),
128.8(Z), 131.8, 132.0, 133.6(Z), 136.9, 139.0, 159.0. HRMS (EI) Calcd. for C14H18OS 234.1078,
found 234.1082.
(2ꢀCyclohexylvinyl)(4ꢀmethoxyphenyl)sulfane. 3k, yellow oil, was obtained as a mixture of
1
stereoisomers in 64:36 (E/Z) ratio (92%, 57.1mg). H NMR (500 MHz, CDCl3) δ 1.02ꢀ1.65 (m,
6H (Eꢀ3k), 6H (Zꢀ3k)), 1.66ꢀ1.68 (m, 4H (Eꢀ3k), 4H (Zꢀ3k)), 1.97ꢀ1.99 (m, 1H, Eꢀ3k), 2.38ꢀ2.40
(m, 1H, Zꢀ3k), 3.73 (s, 3H (Eꢀ3k), 3H (Zꢀ3k)), 5.46ꢀ5.50 (m, 1H, Zꢀ3k), 5.69ꢀ5.73 (m, 1H, Eꢀ3k),
5.92ꢀ5.97 (m, 1H (Eꢀ3k), 1H (Zꢀ3k)), 6.77ꢀ6.80 (m, 2H (Eꢀ3k), 2H (Zꢀ3k)), 7.15ꢀ7.25 (m, 2H
(Eꢀ3k), 2H (Zꢀ3k)). 13C NMR (125 MHz, CDCl3) δ 25.9, 26.0, 26.2, 32.6, 32.9, 38.4 (Z), 41.4,
55.48, 114.8, 121.0, 123.1 (Z), 126.5(Z), 131.9, 132.0, 137.2 (Z), 140.1, 159.0. HRMS (EI) Calcd.
for C15H20OS 248.1235, found 248.1234.
(E)ꢀ2ꢀ(2ꢀ((4ꢀmethoxyphenyl)thio)vinyl)pyridine. Eꢀ3l, yellow solid, m.p. 95ꢀ97 oC (72%, 43.7 mg).
1H NMR (CDCl3, 500 MHz) δ 3.83 (s, 3H), 6.36 (d, J = 15.0 Hz, 1H), 6.92 (d, J = 8.5 Hz, 2H),
7.03ꢀ7.08 (m, 2H), 7.44ꢀ7.50 (m, 3H), 7.56 (t, J = 8.0Hz, 1H), 8.47 (s, 1H). 13C NMR (CDCl3, 125
MHz) δ 55.5, 115.2, 121.2, 121.5, 123.1, 125.8, 132.9, 134.8, 136.6, 149.6, 155.0, 160.2. HRMS
(EI) Calcd. for C14H13NOS 243.0718, found 243.0724.
o
(E)ꢀ3ꢀ(2ꢀ((4ꢀmethoxyphenyl)thio)vinyl)pyridine. Eꢀ3m, yellow solid, m.p. 116ꢀ118 C (90%,
1
54.7 mg). H NMR (CDCl3, 500 MHz) δ 3.84 (s, 3H), 6.35 (d, J = 15.5 Hz, 1H), 6.90ꢀ6.94 (m,
3H), 7.19ꢀ7.21 (m, 1H), 7.42ꢀ7.44 (m, 2H), 7.57ꢀ7.59 (m, 1H), 8.40ꢀ8.49 (m, 2H). 13C NMR
(CDCl3, 125 MHz) δ 55.5, 115.2, 123.3, 123.6, 123.9, 129.3, 132.2, 132.7, 134.4, 147.6, 148.0,
160.1. HRMS (EI) Calcd. for C14H13NOS 243.0718, found 243.0714.
2ꢀ(2ꢀ((4ꢀChlorophenyl)thio)vinyl)thiophene.22 3n, yellow oil, was obtained as a mixture of
stereoisomers in 15:85 (E/Z) ratio (89%, 56.1mg). 1H NMR (500 MHz, CDCl3) δ 6.33 (d, J = 10.0
Hz, 1H (Zꢀ3n)), 6.65 (d, J = 15.0 Hz, 1H (Eꢀ3n)), 6.87ꢀ6.90 (m, 1H (Zꢀ3n), 1H (Eꢀ3n)), 6.95ꢀ7.00
(m, 2H, Eꢀ3n), 7.07ꢀ7.08 (m, 1H, Zꢀ3n), 7.19 (d, J = 4.0 Hz, 1H (Zꢀ3n), 1H (Eꢀ3n)), 7.32ꢀ7.34 (m,
3H (Eꢀ3n), 2H (Zꢀ3n)), 7.36 (d, J = 5.0 Hz, 1H (Zꢀ3n)), 7.40ꢀ7.41 (m, 2H (Zꢀ3n), 1H (Eꢀ3n)). 13
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NMR (125 MHz, CDCl3) δ 122.0, 122.6, 124.8 (E), 125.7 (E), 126.6, 127.1, 127.7 (E), 128.5,
129.5, 131.1, 133.4, 134.4, 139.8. GCꢀMS (EI) m/z: 252.
Phenyl(styryl)sulfane.23 3o, yellow oil, was obtained as a mixture of stereoisomers in 88:12 (E/Z)
ratio (72%, 38.2mg). 1H NMR (CDCl3, 500 MHz) δ 6.53 (d, J = 11.0 Hz, 1H (Zꢀ3o)), 6.62 (d, J =
11.0 Hz, 1H (Zꢀ3o)), 6.76 (d, J = 15.5 Hz, 1H (Eꢀ3o)), 6.91 (d, J = 15.5 Hz, 1H (Eꢀ3o)), 7.24ꢀ7.27
(m, 2H (Zꢀ3o), 1H (Eꢀ3o)), 7.29 (d, J = 7.5 Hz, 1H (Eꢀ3o)), 7.32ꢀ7.38 (m, 6H, Eꢀ3o), 7.41 (d, J =
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8.0 Hz, 2H (Zꢀ3o)), 7.44 (d, J = 7.0 Hz, 2H (Eꢀ3o)), 7.49 (d, J = 7.5 Hz, 2H (Zꢀ3o)), 7.52 (d, J =
7.0 Hz, 2H (Zꢀ3o)), 7.56 (d, J = 7.5 Hz, 2H (Zꢀ3o)). 13C NMR (CDCl3, 125 MHz) δ 123.6, 126.2,
127.1, 127.3 (Z), 127.7, 128.5 (Z), 128.8, 129.3, 130.0, 130.2 (Z), 132.0, 135.4, 136.7. GCꢀMS (EI)
m/z: 212.
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Mesityl(styryl)sulfane. 3p, light yellow oil, was obtained as a mixture of stereoisomers in 90:10
(E/Z) ratio (92%, 58.4 mg). 1H NMR (CDCl3, 500 MHz) δ 2.35 (s, 3H, Zꢀ3p), 2.37 (s, 3H, Eꢀ3p),
2.52 (s, 6H (Eꢀ3p), 6H (Zꢀ3p)), 6.01ꢀ6.05 (m, 1H (Eꢀ3p), 1H (Zꢀ3p)), 6.48 (d, J = 10.5 Hz, 1H
(Zꢀ3p)), 6.71 (d, J = 15.5 Hz, 1H (Eꢀ3p)), 7.02ꢀ7.05 (m, 2H (Eꢀ3p), 2H (Zꢀ3p)), 7.17ꢀ7.20 (m, 1H,
Eꢀ3p), 7.24 (d, J = 7.0 Hz, 2H (Eꢀ3p)), 7.27ꢀ7.30 (m, 2H (Eꢀ3p), 1H (Zꢀ3p)), 7.44ꢀ7.47 (m, 2H,
Zꢀ3p), 7.66 (d, J = 7.5 Hz, 2H (Zꢀ3p)). 13C NMR (CDCl3, 125 MHz) δ 21.3, 21.8 (2C), 22.2 (Z),
125.1, 125.2, 125.4 (Z), 125.6, 126.6 (Z), 126.7, 128.5 (Z), 128.7, 128.9, 129.4 (Z), 129.5, 137.3,
139.0 (Z), 139.4, 142.4 (Z), 143.3 (2C). HRMS (EI) Calcd. for C17H18S 254.1129, found
254.1130.
Styryl(oꢀtolyl)sulfane.24 3q, light yellow oil, was obtained as a mixture of stereoisomers in 90:10
(E/Z) ratio (90%, 50.9 mg). 1H NMR (CDCl3, 500 MHz) δ 2.36 (s, 3H, Eꢀ3q), 2.39 (s, 3H, Zꢀ3q),
6.32 (d, J = 11.0 Hz, 1H (Zꢀ3q)), 6.52ꢀ6.55 (m, 1H (Eꢀ3q), 1H (Zꢀ3q)), 6.76 (d, J = 15.5 Hz, 1H
(Eꢀ3q)), 7.13ꢀ7.19 (m, 4H (Eꢀ3q), 4H (Zꢀ3q)), 7.22ꢀ7.27 (m, 4H (Eꢀ3q), 2H (Zꢀ3q)), 7.32ꢀ7.36 (m,
1H (Eꢀ3q), 1H (Zꢀ3q)), 7.52 (d, J = 7.5 Hz, 2H (Zꢀ3q)). 13C NMR (CDCl3, 125 MHz) δ 20.5,
123.5, 126.1 (2C), 126.5 (Z), 126.9, 127.6 (2C), 128.4 (Z), 128.8 (2C), 130.6, 131.1 (2C), 133.9,
136.8, 138.9. GCꢀMS (EI) m/z: 226.
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(4ꢀChlorophenyl)(styryl)sulfane.25 3r, light yellow oil, was obtained as a mixture of stereoisomers
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in 82:18 (E/Z) ratio (96%, 59.0 mg). H NMR (CDCl3, 500 MHz) δ 6.44 (d, J = 11.0 Hz, 1H
(Zꢀ3r)), 6.64 (d, J = 10.5 Hz, 1H (Zꢀ3r)), 6.76 (d, J = 15.0 Hz, 1H (Eꢀ3r)), 6.84 (d, J = 15.5 Hz,
1H (Eꢀ3r)), 7.26ꢀ7.43 (m, 9H (Eꢀ3r), 7H (Zꢀ3r)), 7.53ꢀ7.54 (m, 2H, Zꢀ3r). 13C NMR (CDCl3, 125
MHz) δ 122.7, 125.3 (Z), 126.3, 127.5 (Z), 128.0, 128.2 (Z), 128.5, 128.9, 129.4, 131.1, 131.4,
132.9, 133.2 (Z), 134.0 (Z), 136.4. GCꢀMS (EI) m/z: 246.
(2ꢀBromophenyl)(styryl)sulfane.26 3s, light yellow oil, was obtained as a mixture of stereoisomers
in 50:50 (E/Z) ratio (82%, 59.4mg). 1H NMR (500 MHz, CDCl3) δ 6.43 (d, J = 10.5 Hz, 1H
(Zꢀ3s)), 6.78 (d, J = 10.5 Hz, 1H (Zꢀ3s)), 6.85 (d, J = 15.5 Hz, 1H (Eꢀ3s)), 6.94 (d, J = 15.5 Hz,
1H (Eꢀ3s)), 7.09ꢀ7.29 (m, 1H (Zꢀ3s), 1H (Eꢀ3s)), 7.30ꢀ7.62 (m, 8H (Eꢀ3s), 8H (Zꢀ3s)). 13C NMR
(125 MHz, CDCl3) δ 121.0 (Z), 123.1 (Z), 123.8, 124.3, 126.5 (Z), 127.6, 127.7 (Z), 128.2, 128.3,
128.5, 128.9, 129.1 (Z), 130.1, 130.5, 133.2, 135.6 (Z), 136.2, 136.4 (Z), 137.7. GCꢀMS (EI) m/z:
290.
(E)ꢀ(4ꢀmethoxyphenyl)(styryl)sulfane.27 3t, light yellow oil, was obtained as a mixture of
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stereoisomers in 89:11 (E/Z) ratio (91%, 55.1 mg). H NMR (CDCl3, 500 MHz) δ 3.75 (s, 3H,
Zꢀ3t), 3.76 (s, 3H, Eꢀ3t), 6.34 (d, J = 11.0 Hz, 1H (Zꢀ3t)), 6.42ꢀ6.47 (m, 1H (Eꢀ3t), 1H (Zꢀ3t)),
6.76 (d, J = 15.5Hz, 1H (Eꢀ3t)), 6.82ꢀ6.86 (m, 2H (Eꢀ3t), 2H (Zꢀ3t)), 7.12ꢀ7.16 (m, 1H, Eꢀ3t),
7.19ꢀ7.23 (m, 4H (Eꢀ3t), 2H (Zꢀ3t)), 7.31ꢀ7.37 (m, 2H (Eꢀ3t), 3H (Zꢀ3t)), 7.46 (d, J = 7.5Hz, 2H
(Zꢀ3t)). 13C NMR (CDCl3, 125 MHz) δ 55.5, 115.1, 124.7, 125.9, 126.0, 127.1 (Z), 127.3, 128.4
(Z), 128.8, 129.2, 133.1 (Z), 133.6, 136.9, 159.7. GCꢀMS (EI) m/z: 242.
(4ꢀChlorophenethyl)(pꢀtolyl)sulfane.28 4a, yellow oil (87%, 57.0 mg). 1H NMR (CDCl3, 500 MHz)
δ 2.34 (s, 3H), 2.87 (t, J = 8.0 Hz, 2H), 3.09ꢀ3.12 (m, 2H), 7.11ꢀ7.14 (m, 4H), 7.25ꢀ7.29 (m, 4H).
13C NMR (CDCl3, 125 MHz) δ 21.2 (2C), 35.5, 36.1, 128.6, 129.3, 129.9, 130.2, 132.8, 136.1,
136.3, 137.5. GCꢀMS (EI) m/z: 262.
(4ꢀMethylphenethyl)(pꢀtolyl)sulfane.29 4b, light yellow oil (90%, 54.5 mg). 1H NMR (CDCl3, 500
MHz) δ 2.41 (s, 6H), 2.96 (t, J = 8.0 Hz, 2H), 3.20 (t, J = 8.0 Hz, 2H), 7.15ꢀ7.21 (m, 6H), 7.37 (d,
J = 8.0 Hz, 2H). 13C NMR (CDCl3, 125 MHz) δ 21.2 (2C), 35.5, 36.1, 128.6, 129.3, 129.9, 130.2,
132.8, 136.1, 136.3, 137.5. GCꢀMS (EI) m/z: 242.
(4ꢀBromophenethyl)(pꢀtolyl)sulfane.30 4c, light yellow oil (80%, 61.2 mg). 1H NMR (CDCl3, 500
MHz) δ 2.33 (s, 3H), 2.85 (t, J = 7.5 Hz, 2H), 3.08ꢀ3.11 (m, 2H), 7.05 (d, J = 8.5 Hz, 2H), 7.12 (d,
J = 8.0 Hz, 2H), 7.27 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H). 13C NMR (CDCl3, 125 MHz) δ
21.1, 35.2, 35.9, 120.3, 129.9, 130.4, 130.5, 131.7, 132.3, 136.6, 139.3. GCꢀMS (EI) m/z: 306.
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pꢀTolyl(2,4,6ꢀtrimethylphenethyl)sulfane. 4d, yellow oil (96%, 64.8 mg). H NMR (CDCl3, 500
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MHz) δ 2.29ꢀ2.32 (m, 9H), 2.41 (s, 3H), 2.93ꢀ3.02 (m, 4H), 6.90 (s, 2H), 7.20 (d, J = 8.5 Hz, 2H),
7.41 (d, J = 8.0 Hz, 2H). 13C NMR (CDCl3, 125 MHz) δ 19.8, 21.0, 21.2, 30.0, 33.6, 129.2, 129.9,
130.8, 132.7, 134.2, 135.9, 136.3, 136.6. HRMS (EI) Calcd. for C18H22S 270.1442, found
270.1440.
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(4ꢀChlorophenyl)(2,2ꢀdiphenylethyl)sulfane. 4e, yellow solid, m.p. 84ꢀ86 C (lit. 85ꢀ87 C, 79%,
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64.0 mg). H NMR (CDCl3, 500 MHz) δ 3.60 (d, J = 8.0 Hz, 2H), 4.21 (t, J = 8.0 Hz, 1H),
7.23ꢀ7.26 (m, 10H), 7.27ꢀ7.34 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 40.1, 50.8, 127.0, 128.1
(4C), 128.8 (4C), 129.2, 131.0, 132.2, 135.2, 143.0. HRMS (EI) Calcd. for C20H17ClS 324.0739,
found 324.0741.
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(2,2ꢀDiphenylethyl)(pꢀtolyl)sulfane.30 4f (radical trapping product C), yellow oil (83%, 63.1 mg).
1H NMR (CDCl3, 500 MHz) δ 2.32 (s, 3H), 3.55 (d, J = 7.5 Hz, 2H), 4.17 (t, J = 8.0 Hz, 1H), 7.09
(d, J = 8.0 Hz, 2H), 7.20ꢀ7.25 (m, 8H), 7.28ꢀ7.31 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 21.2,
40.5, 50.7, 126.8 (2C), 128.1 (4C), 128.7 (4C), 129.9 (2C), 130.5 (2C), 132.8, 136.4, 143.3 (2C).
GCꢀMS (EI) m/z: 304.
1ꢀBenzylꢀ3ꢀ(pꢀtolylthio)pyrrolidineꢀ2,5ꢀdione.31 4g, yellow oil (52%, 40.4 mg). 1H NMR (CDCl3,
500 MHz) δ 2.42 (s, 3H), 3.00ꢀ3.05 (m, 1H), 3.22ꢀ3.26 (m, 1H), 4.30ꢀ4.33 (m, 1H), 4.56 (s, 2H),
7.25ꢀ7.29 (m, 7H), 7.68 (d, J = 8.5 Hz, 2H). 13C NMR (CDCl3, 125 MHz) δ 21.9, 30.2, 43.1, 63.5,
128.2, 128.8 (4C), 129.4, 130.2, 133.3, 134.9, 146.3, 168.6, 172.9. MS (ESI) m/z: 311.
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(3ꢀ(4ꢀMethoxyphenyl)propyl)(pꢀtolyl)sulfane. 4h, yellow oil (76%, 51.7 mg). H NMR (CDCl3,
500 MHz) δ 1.90ꢀ1.95 (m, 2H), 2.33 (s, 3H), 2.71 (t, J = 7.5 Hz, 2H), 2.89 (t, J = 7.5 Hz, 2H),
3.80 (s, 3H), 6.83ꢀ6.85 (m, 2H), 7.09ꢀ7.11 (m, 4H), 7.24ꢀ7.26 (m, 2H). 13C NMR (CDCl3, 125
MHz) δ 21.1, 31.1, 33.8, 33.9, 55.4, 114.0, 129.5, 129.8, 130.1, 132.9, 133.6, 136.1, 158.0. HRMS
(EI) Calcd. for C17H20OS 272.1235, found 272.1241.
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(3ꢀPhenylpropyl)(pꢀtolyl)sulfane.29 4i, yellow oil (97%, 58.7 mg). H NMR (CDCl3, 500 MHz) δ
1.84ꢀ1.89 (m, 2H), 2.25 (s, 3H), 2.68 (d, J = 7.5 Hz, 2H), 2.78 (t, J = 7.5 Hz, 2H), 7.02 (t, J = 8.0
Hz, 2H), 7.09ꢀ7.13 (m, 3H), 7.16ꢀ7.22 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 21.2, 30.8, 33.8,
34.8, 126.1, 128.5, 128.6, 129.8, 130.2, 132.8, 136.2, 141.5. GCꢀMS (EI) m/z: 242.
(4ꢀChlorophenyl)(octyl)sulfane.32 4j, colorless oil (96%, 53.8 mg). 1H NMR (CDCl3, 500 MHz) δ
0.87 (t, J = 7.0 Hz, 3H), 1.26ꢀ1.30 (m, 8H), 1.37ꢀ1.41 (m, 2H), 1.59ꢀ1.65 (m, 2H), 2.88 (t, J = 7.0
Hz, 2H), 7.23 (s, 4H). 13C NMR (CDCl3, 125 MHz) δ 14.3, 22.8, 28.9, 29.2, 29.3, 29.3, 31.9, 34.0,
129.1, 130.3, 131.7, 135.7. GCꢀMS (EI) m/z: 256.
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(2ꢀbromophenyl)(cyclohexyl)sulfane.33 4k, yellow oil (98%, 66.2 mg). H NMR (CDCl3, 500
MHz) δ 1.78ꢀ1.87 (m, 3H), 2.21ꢀ2.26 (m, 2H), 2.40ꢀ2.52 (m, 4H), 2.74ꢀ2.78 (m, 1H), 3.58ꢀ3.68 (m,
1H), 7.16ꢀ7.19 (m, 1H), 7.31ꢀ7.34 (m, 1H), 7.47ꢀ7.49 (m, 1H), 7.65ꢀ7.67 (m, 1H). 13C NMR
(CDCl3, 125 MHz) δ 24.4, 31.1, 41.0, 45.3, 47.6, 127.6, 128.0, 128.9, 133.4, 134.8, 208.4. GCꢀMS
(EI) m/z: 270.
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bicyclo[2.2.1]heptanꢀ2ꢀyl(pꢀtolyl)sulfane.34 4l, yellow oil (98%, 53.4 mg). H NMR (CDCl3, 500
MHz) δ 1.17ꢀ1.22 (m, 3H), 1.39ꢀ1.43 (m, 1H), 1.51ꢀ1.80 (m, 4H), 2.24ꢀ2.29 (m, 2H), 2.32 (s, 3H),
3.12ꢀ3.15 (m, 1H), 7.09 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H). 13C NMR (CDCl3, 125 MHz)
δ 20.0, 27.7, 27.9, 34.5, 35.5, 37.6, 41.2, 48.0, 128.5, 129.0, 132.8, 134.7. GCꢀMS (EI) m/z: 218.
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2ꢀ(2ꢀ(pꢀtolylthio)ethyl)pyridine.35 4m, yellow oil (95%, 54.4 mg). H NMR (CDCl3, 500 MHz) δ
2.32 (s, 3H), 3.08 (t, J = 8.0 Hz, 2H), 3.29 (t, J = 8.0 Hz, 2H), 7.09ꢀ7.14 (m, 4H), 7.26ꢀ7.29 (m,
2H), 7.57ꢀ7.60 (m, 1H), 8.53ꢀ8.54 (m, 1H). 13C NMR (CDCl3, 125 MHz) δ 21.1, 34.5, 38.0, 121.6,
123.4, 129.8, 130.4, 132.5, 136.4, 136.5, 149.5, 160.0. GCꢀMS (EI) m/z: 229.
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2ꢀ(2ꢀ((4ꢀMethoxyphenyl)thio)ethyl)thiophene. 4n, yellow oil (83%, 51.9 mg). H NMR (CDCl3,
500 MHz) δ 3.07ꢀ3.15 (m, 4H), 3.84 (s, 3H), 6.84ꢀ6.96 (m, 4H), 7.16ꢀ7.17 (m, 1H), 7.40ꢀ7.43 (m,
2H). 13C NMR (CDCl3, 125 MHz) δ 30.2, 37.6, 55.5, 114.8, 123.7, 125.0, 125.9, 126.9, 133.8,
143.0, 159.3. HRMS (EI) Calcd. for C13H14OS2 250.0486, found 250.0484.
1,2ꢀBis(pꢀtolylthio)ethane.36 4o, yellow oil (80%, 54.8 mg). 1H NMR (CDCl3, 500 MHz) δ 2.38 (s,
6H), 3.07 (s, 4H), 7.14 (d, J = 8.0 Hz, 4H), 7.27 (d, J = 8.5 Hz, 4H). 13C NMR (CDCl3, 125 MHz)
δ 21.2, 34.1, 129.9, 130.9, 131.4, 136.9. GCꢀMS (EI) m/z: 274.
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Sꢀ(pꢀtolyl)diphenylphosphinothioate.37 5a, white solid, m.p. 110ꢀ112 C (lit. 112ꢀ113 C, 72%,
58.3 mg). 1H NMR (CDCl3, 500 MHz) δ 2.23 (s, 3H), 7.01 (d, J = 8.0 Hz, 2H), 7.36ꢀ7.38 (m, 2H),
7.41ꢀ7.45 (m, 4H), 7.48ꢀ7.51 (m, 2H), 7.87ꢀ7.90 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 21.3,
122.3, 128.6, 128.7, 130.1, 131.7, 131.8, 132.2, 132.5, 133.1, 135.5, 139.4. 31P NMR (CDCl3, 202
MHz): δ 42.0. GCꢀMS (EI) m/z: 324.
Sꢀ(pꢀtolyl)diꢀpꢀtolylphosphinothioate. 5b, white solid, m.p. 145ꢀ147 C (69%, 60.1 mg). 1H NMR
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(CDCl3, 500 MHz) δ 2.29 (s, 3H), 2.41 (s, 6H), 7.05 (d, J = 8.0 Hz, 2H), 7.27ꢀ7.29 (m, 4H),
7.36ꢀ7.38 (m, 2H), 7.75ꢀ7.79 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 21.3, 21.8, 122.8, 129.3,
129.4, 130.1, 131.7, 131.8, 135.4, 139.1, 142.9. 31P NMR (CDCl3, 202 MHz): δ 42.2. HRMS (ESI)
Calcd. for C21H21OPSH+ 353.1129, found [M+H]+ 353.1139.
Sꢀ(pꢀtolyl)bis(4ꢀfluorophenyl)phosphinothioate. 5c, white solid, m.p. 127ꢀ129 oC (75%, 67.7 mg).
1H NMR (CDCl3, 500 MHz) δ 2.26 (s, 3H), 7.01ꢀ7.03 (d, J = 8.0 Hz, 2H), 7.11ꢀ7.15 (m, 4H),
7.29ꢀ7.30 (d, J = 6.5 Hz, 2H), 7.81ꢀ7.85 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 21.3,
116.0ꢀ116.3 (d, J = 4C), 121.9, 128.1, 129.0, 130.2, 134.0ꢀ134.4 (4C), 135.4, 139.6, 164.4ꢀ166.4
(d, J = 254.8 Hz, 2C). 31P NMR (CDCl3, 202 MHz): δ 39.4. HRMS (ESI) Calcd. for
C19H15F2OPSNa+ 383.0447, found [M+Na]+ 383.0457.
Sꢀ(pꢀtolyl)bis(4ꢀ(trifluoromethyl)phenyl)phosphinothioate. 5d, white solid, m.p. 132ꢀ134 oC (76%,
87.4 mg). 1H NMR (CDCl3, 500 MHz) δ 2.28 (s, 3H), 7.05 (d, J = 8.0 Hz, 2H), 7.31ꢀ7.33 (m, 2H),
7.71ꢀ7.73 (m, 4H), 7.96ꢀ8.00 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 21.3, 120.3ꢀ126.8 (q, J =
271.3 Hz, 2C) 120.7, 122.4, 124.6, 125.7, 125.8, 130.4, 132.1, 132.3, 134.1ꢀ134.9 (q, J = 32.5 Hz,
2C), 135.6, 136.1, 136.9, 140.1. 31P NMR (CDCl3, 202 MHz): δ 37.9. HRMS (ESI) Calcd. for
C21H15F6OPSNa+ 483.0383, found [M+Na]+ 483.0394.
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Sꢀ(pꢀtolyl)di(naphthalenꢀ2ꢀyl)phosphinothioate. 5e, white solid, 159ꢀ161 C (60%, 63.3 mg). H
NMR (CDCl3, 500 MHz) δ 2.22 (s, 3H), 6.97 (d, J = 8.0 Hz, 2H), 7.40ꢀ7.43 (m, 4H), 7.48ꢀ7.52 (m,
4H), 7.85ꢀ7.87 (m, 2H), 7.97 (d, J = 8.5 Hz, 2H), 8.06ꢀ8.11 (m, 2H), 8.91ꢀ8.93 (m, 2H). 13C NMR
(CDCl3, 125 MHz) δ 21.3, 123.3, 124.5, 124.6, 126.7, 127.4, 127.5, 128.8, 129.0, 129.7, 130.0,
133.4, 133.5, 133.6, 133.7, 133.9, 134.0, 134.1, 135.5, 139.2. 31P NMR (CDCl3, 202 MHz): δ 45.5.
HRMS (ESI) Calcd. for C27H21OPSNa+ 447.0948, found [M+Na]+ 447.0960.
Sꢀ(4ꢀchlorophenyl)diphenylphosphinothioate.1e 5f, white solid, m.p. 99ꢀ101 C (lit. 103ꢀ104 C,
o
o
1
81%, 69.7 mg). H NMR (CDCl3, 500 MHz) δ7.16 (d, J = 8.5 Hz, 2H), 7.35ꢀ7.44 (m, 2H),
7.44ꢀ7.46 (m, 4H), 7.50ꢀ7.53 (m, 2H), 7.81ꢀ7.85 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 124.9,
128.7, 128.8, 129.5, 131.7, 131.8, 131.9, 132.6, 132.8, 135.7, 136.7. 31P NMR (CDCl3, 202 MHz):
δ 41.7. GCꢀMS (EI) m/z: 344.
Sꢀ(4ꢀmethoxyphenyl)diphenylphosphinothioate.1e 5g, white solid, m.p. 141ꢀ143 C, (lit. 140ꢀ142
o
oC, 62%, 52.7 mg). H NMR (CDCl3, 500 MHz) δ 3.74 (s, 3H), 6.73 (d, J = 7.5 Hz, 2H),
1
7.32ꢀ7.34 (m, 2H), 7.44ꢀ7.46 (m, 4H), 7.50ꢀ7.53 (m, 2H), 7.82ꢀ7.86 (m, 4H). 13C NMR (CDCl3,
125 MHz) δ 55.4, 114.9, 116.1, 128.6, 128.7, 131.7, 131.8, 132.4, 133.2, 137.2, 160.0. 31P NMR
(CDCl3, 202 MHz): δ 41.6. GCꢀMS (EI) m/z: 340.
Sꢀ(4ꢀbromophenyl) diphenylphosphinothioate.38 5h, white solid, m.p. 148ꢀ150 oC (lit. 151ꢀ153 oC,
70%, 67.9 mg). 1H NMR (CDCl3, 500 MHz) δ 7.31 (s, 4H), 7.42ꢀ7.46 (m, 4H), 7.50ꢀ7.53 (m, 2H),
7.82ꢀ7.86 (m, 4H). 13C NMR (CDCl3, 125 MHz) δ 123.9, 125.5, 128.7, 128.9, 131.7, 131.8 (3C),
132.4 (3C), 132.7, 136.9 (2C). 31P NMR (CDCl3, 202 MHz): δ 41.7. GCꢀMS (EI) m/z: 388.
O,OꢀdiethylꢀSꢀ(pꢀtolyl)phosphorothioate.39 5i, colorless oil (71%, 46.2 mg). 1H NMR (CDCl3, 500
MHz) δ 1.30 (t, J = 7.0 Hz, 6H), 2.33 (s, 3H), 4.11ꢀ4.23 (m, 4H), 7.14 (d, J = 8.0 Hz, 2H),
7.42ꢀ7.44 (m, 2H). 13C NMR (CDCl3, 125 MHz) δ 16.2 (2C), 21.3, 64.1 (2C), 123.0, 130.3, 134.7,
139.4. 31P NMR (CDCl3, 202 MHz): δ 23.5. GCꢀMS (EI) m/z: 260.
Sꢀ(4ꢀmethoxyphenyl)ꢀO,Oꢀdiphenyl phosphorothioate.40 5j, colorless oil (78%, 72.5 mg). 1H
NMR (CDCl3, 500 MHz) δ 3.80 (s, 3H), 6.85 (d, J = 8.5 Hz, 2H), 7.19ꢀ7.22 (m, 6H), 7.33ꢀ7.39 (m,
6H). 13C NMR (CDCl3, 125 MHz) δ 55.6, 115.2 (2C), 120.6 (4C), 125.6 (2C), 129.9 (5C), 137.2
(2C), 150.5, 150.6, 161.1. 31P NMR (CDCl3, 202 MHz): δ 15.6. GCꢀMS (EI) m/z: 372.
Sꢀmethyl diphenylphosphinothioate. 5k, colorless oil (30%, 18.6 mg). 1H NMR (CDCl3, 500 MHz)
δ 2.17 (d, J = 12.0 Hz, 3H), 7.41ꢀ7.44 (m, 4H), 7.47ꢀ7.50 (m, 2H), 7.79ꢀ7.84 (m, 4H). 13C NMR
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(CDCl3, 125 MHz) δ 9.57, 127.7, 127.8, 130.5, 130.6, 131.3 (2C), 132.2 (2C). 31P NMR (CDCl3,
202 MHz): δ 44.5. HRMS (EI) Calcd. for C13H13OPS 248.0425, found 248.0418.
2,2,6,6ꢀTetramethylꢀ1ꢀ((pꢀtolylthio)oxy)piperidine.41 A, white solid, m.p. 62ꢀ64 oC. 1H NMR (500
MHz, CDCl3) δ 1.50 (s, 12H), 1.59 (s, 6H), 2.32 (s, 3H), 7.15ꢀ7.17 (d, J = 8.0 Hz. 2H), 7.66ꢀ7.67
(d, J = 8.0 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 17.9, 22.5, 32.2, 45.0, 61.8, 127.3, 130.2,
142.8, 145.7. MS (ESI) m/z: 280 [M+H]+.
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Supporting Information
Mechanism experiments, quantum chemical calculations and copies of NMR
spectra of all products. This material is available free of charge via the Internet
at http://pubs.acs.org.
Acknowledgements
We gratefully acknowledge the Natural Science Foundation of China
(21402093, 21476116) and Jiangsu (BK20140776, BK20141394), Chinese
Postdoctoral Science Foundation (2016T90465, 2015M571761) and the Center
for Advanced Materials and Technology in Nanjing University of Science and
Technology for financial support.
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