Iron/copper Co-catalyzed synthesis of vinyl sulfones from sulfonyl hydrazides and alkyne derivatives

Article abstract of DOI:10.1021/acs.joc.5b00558

A new approach to the selective synthesis of (E)-vinyl sulfones has been developed via a Fe/Cu co-catalyzed sulfonylation of arylpropiolic acid or phenylacetylene with sulfonyl hydrazides. A variety of vinyl sulfones have been obtained in moderate to good yields, comparable to the best results reported so far. The inexpensive Fe/Cu co-catalyzed method features a simple experimental procedure and good tolerance of substrate.

Full text of DOI:10.1021/acs.joc.5b00558

Article
pubs.acs.org/joc
Iron/Copper Co-Catalyzed Synthesis of Vinyl Sulfones from Sulfonyl
Hydrazides and Alkyne Derivatives
Guangwei Rong,† Jincheng Mao,*,†,‡ Hong Yan,† Yang Zheng,† and Guoqi Zhang*,§
†Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering, and Materials Science,
Soochow University, Suzhou 215123, P. R. China
‡State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, P. R.
China
§Department of Sciences, John Jay College and The Graduate Center, The City University of New York, New York, New York 10019,
United States
S
* Supporting Information
ABSTRACT: A new approach to the selective synthesis of (E)-vinyl sulfones has been developed via a Fe/Cu co-catalyzed
sulfonylation of arylpropiolic acid or phenylacetylene with sulfonyl hydrazides. A variety of vinyl sulfones have been obtained in
moderate to good yields, comparable to the best results reported so far. The inexpensive Fe/Cu co-catalyzed method features a
simple experimental procedure and good tolerance of substrate.
Alternatively, vinyl sulfones can also be achieved through the
addition of sulfone radical to alkyne.4 Relevant work has been
reported more recently by Wang and co-workers who
introduced a copper-catalyzed selective hydrosulfonylation of
alkynes with arylsulfinic acids (Figure 1).4a Yet this method
suffers from major issues such as limited substrate scope and
poor stability and availability of sulfinic acid. In the same year,
Jiang group revealed a chemoselective synthesis of unsym-
metrical internal alkynes or vinyl sulfones via palladium-
catalyzed cross-coupling reaction of sodium sulfinates with
alkynes.4c In contrast, the latter protocol shows better
functional group tolerance for a wide range of alkynes including
aliphatic substrates. However, the use of precious metal
palladium as a catalyst will necessarily increases the cost of
this procedure, and therefore, it would be less likely to be
employed for large-scale applications, in particular in industrial
manufacturing. Recent research has addressed the importance
of the replacement of precious metals (Pd, Pt, or Ru) with
earth-abundant catalysts containing iron, copper, or cobalt in
the fields of chemical synthesis and energy conversion.5
Consequently, major progress has been made in earth-abundant
metal-catalyzed reactions, and in particular, copper and iron
catalysts have found widespread applications in decarboxylation
reactions of phenylpropiolic acids.6
INTRODUCTION
■
Vinyl sulfones have attracted considerable interests in the area
of synthetic organic chemistry in recent years, owing to their
important role in serving as key structural units of many
biological active compounds or medicines1 as well as versatile
building blocks for various organic transformations.2 An
overview of previously related work on the preparation of
such vinyl sulfones resulted in the finding that generally the
sulfone unit of this compound could be originated from
sulfonyl chloride, sulfinic acid, sodium sulfinate, and sulfonyl
hydrazide, of which sodium sulfinate and sulfonyl hydrazide
have been predominantly utilized, probably due to their good
stability and ease of handling. On the other hand, styrene and
cinnamic acid derivatives were popularly chosen as the reaction
partners to provide the alkene moiety. The main methodologies
that were recently developed for the synthesis of vinyl sulfones
have been illustrated in Figure 1. In 2001, a facile one-pot
synthesis of vinyl sulfones via a CAN-mediated reaction of aryl
sulfinates and alkenes was reported by the Nair group, and
similar works were independently revealed by the Chutima
group and others by using potassium iodide or iodine as
catalysts.3a−d Very recently, Jiang group proposed an alternative
way to prepare vinyl sulfones through a catalytic reaction
between styrene and benzenesulfonyl hydrazide using copper-
(I) chloride as a catalyst.3e Relevant results on the
decarboxylative sulfonylation of cinnamic acids with sodium
sulfinates have been reported by Guo and Jiang groups,
respectively, according to two different protocols, while Jiang’s
approach has advantages of transition-metal-free reaction
conditions and relatively higher yields over the Guo’s one.3e−g
However, the combination of two kinds of earth-abundant
metals as effective catalyst systems was only scarcely explored
very recently, in a few types of reactions.7 Herein, we wish to
Received: March 15, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.5b00558
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Figure 1. Diverse approaches to prepare useful vinyl sulfones.
a
Table 1. Catalytic Decarboxylative and Dehydrazine Reactions between Phenylpropiolic Acids and Sulfonyl Hydrazide
entry
catalyst
additive
oxidant
solvent
yield (%)
1
2
CuI
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
Dioxane
Etanol
45
29
27
41
25
38
60
22
34
NR
67
64
68
51
52
63
70
75
81
57
61
NR
Cu
3
CuO
CuBr
CuBr2
CuSO4
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
CuAy
−
4
5
6
7
8
9
−
−
10
11
12
13
14
15
16
17
CH3CN
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
FeCl3
TBHP
TBHP
TBHP
TBHP
DCP
TBPB
DTBP
DTBP
DTBP
−
TBAI
FeCl2·4H2O
Fe
FeCl2·4H2O
FeCl2·4H2O
FeCl2·4H2O
FeCl2·4H2O
FeCl2·4H2O
FeCl2·4H2O
−
b
18
bc
,
19
20
21
22
DTBP
FeCl2·4H2O
DTBP
a
Reaction conditions: Phenylpropiolic acid 1a (0.3 mmol), 4-methylbenzenesulfonhydrazide 2a (0.6 mmol), copper acrylate (20 mol %), DMSO (2
mL), additive (10 mol %), oxidant (0.6 mmol), 100 °C, 12 h, air. DTBP: tert-butyl peroxide; TBHP: tert-butyl hydroperoxide; DCP: dicumyl
b
c
peroxide. CuAy: copper acrylate. Additive (15 mol %). Oxidant (0.9 mmol).
report our findings of novel Cu/Fe co-catalyzed sulfonylation
of aromatic propiolic acids with sulfonyl hydrazides via a
combined decarboxylative and dehydrazine process. In
addition, similar reactions were carried out by replacing
propiolic acids with aryl acetylenes. A variety of (E)-vinyl
sulfones have been selectively accessed in reasonable yields.
(2a; 2.0 equiv) in the presence of CuI (20 mol %) in dimethyl
sulfoxide (DMSO) at 100 °C for 12 h, and to our delight the
desired vinyl sulfone 3a was harvested in 45% yield as shown in
Table 1 (entry 1). Subsequently, various copper salts such as
cupric oxide, cuprous bromide, and copper acrylate were tested
as the catalysts, copper acrylate was proved to be the best
choice, and the target product 3a was selectively achieved in
60% yield with an E configuration (entries 2−7, Table 1 and
SI). Other solvents than DMSO usually dropped the yield to a
much lower level (entries 8−10 and SI). In order to further
RESULTS AND DISCUSSION
■
We initially started our investigation by choosing phenyl-
propiolic acid (1a) to react with p-toluenesulfonyl hydrazide
B
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a
Table 2. Substrate Scope of the Reactions between Aromatic Propiolic Acids and Sulfonyl Hydrazides
a
Reaction conditions: Phenylpropiolic acid 1 (0.3 mmol), benzenesulfonhydrazide 2 (0.6 mmol), copper acrylate (20 mol %), FeCl2·4H2O (15 mol
%), DTBP (0.9 mmol), DMSO (2 mL), 100 °C, air.
improve the results, we next attempted to use different types of
additives, except for the copper acrylate catalyst. Some organic
or inorganic bases (Na2CO3, Et3N, etc.), co-ligands (such as
PPh3 and L-proline), and extra iron catalysts in the presence of
various oxidants have been screened (Table 1 and SI for
details), and it was pleasing to find that when a second metal
catalyst FeCl2·4H2O (10 mol %) and an oxidant TBHP (2.0
equiv) were added into the reaction, the yield was increased to
68% (entries 11−17, Table 1). Furthermore, the reaction was
promoted with increased amount of FeCl2·4H2O (15 mol %)
and the oxidant DTBP (3.0 equiv), affording 3a in 81% yield.
The controlled experiments revealed that the concurrent
addition of both the copper/iron catalyst and oxidant is crucial
for an improved conversion of the starting materials (entries
20−22, Table 1), highlighting the importance of copper/iron
catalysis in the present reaction. Although we were unable to
further improve the yield of 3a through a thorough screening of
reaction conditions (see SI), the yield obtained is well
comparable to the best results for the synthesis of vinyl
sulfones that were reported heretofore.3,4
With the optimized reaction conditions in hand, we sought
to expand the substrate scope that is applicable for the current
reaction. Therefore, a range of substituted aromatic propiolic
acids and benzenesulfonyl hydrazides were chosen to react with
the Cu/Fe co-catalyst, and the results are summarized in Table
2. It was found that moderate to good yields ranging from 30%
to 81% for a variety of vinyl sulfones were achieved. Although
phenylpropiolic acids bearing strong electron-withdrawing
groups (−CF3 and −CN) on the benzene rings led to the
corresponding products in slightly lower yields (3c, 3l),
halogen or alkyl substitution generally favored the conversion
under standard conditions giving the products in good yields,
except that an ortho-chloro substituent lowered the yield to
30% (3h), because probably of increasing steric hindrance. This
was further confirmed by the fact that only trace amount of 3i
was detected when the bulky 3-(naphthalen-1-yl)propiolic acid
C
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a
Table 3. Cu/Fe Catalytic Synthesis of Vinyl Sulfones from Aromatic alkynes and p-Toluenesulfonyl Hydrazides
a
Reaction conditions: Phenylacetylene 4 (0.3 mmol), 4-methylbenzenesulfonhydrazide 2a (0.6 mmol), copper acrylate (20 mol %), FeCl2·4H2O (15
b
mol %), DTBP (0.9 mmol), DMSO (2 mL), 100 °C, air. In the absence of FeCl2·4H2O.
Scheme 1. Reactivity Tests by a Radical Scavenger
was employed to the reaction with p-toluenesulfonyl hydrazide,
while the ortho-position free 3-(naphthalen-2-yl)propiolic acid
furnished the reaction in 66% yield (3j).
products in moderate to good yields, with exclusively E isomers
obtained (Table 3). For example, substrates with alkyl and halo
substituents furnished the reactions with desired products in
yields ranging from 56% to 81%. Heterocyclic alkynes were also
suitable substrates for this transformation and the correspond-
ing vinyl sulfones were obtained in 80% and 62% yields,
respectively (3u, 3v).
In order to gain insights into the reaction details on the Cu/
Fe catalytic reactions, further reactivity tests were performed by
introducing TEMPO, a common radical scavenger into the
reaction mixtures of p-toluenesulfonyl hydrazide with either
phenylpropiolic acid or phenylacetylene under standard
conditions (Scheme 1). After 12 h reactions at 100 °C,
however, only a trace amount of product 3a was detected in
both cases, and the starting materials were recycled, indicating
that the reactions were almost completely inhibited by TEMPO
(4 equiv). This strongly suggests that the reactions have
proceeded through a radical mechanism.
Based on previous reports on relevant reaction as well as our
own findings as described above, we proposed a plausible
reaction mechanism for the bimetallic Cu/Fe catalytic reaction.
The reaction is likely to be initiated by a single-electron transfer
between 2a and FeII/CuII species in the presence of the oxidant
DTBP to give an unstable cation radical A, which readily loses a
proton to generate a new radical B. Radical B then undergoes
similar deprotonation assisted by the FeII/CuII species, resulting
in the formation of an azo radical C. Subsequently, a sulfonyl
On the other hand, various substituted benzenesulfonyl
hydrazides were also explored under optimal conditions.
Likewise, reactions involving electron-withdrawing groups
including halos were run slightly more sluggishly, generating
the corresponding products in 41−42% yields after 12 h. Good
yields were obtained when substrates with methoxyl or
naphthyl substitutents were applied to the reaction with
phenylpropiolic acid under the same conditions.
Encouraged by the results depicted above, we also attempted
to extend our Cu/Fe co-catalysis system to a similar
transformation for the synthesis of vinyl sulfones, yet utilizing
aryl alkynes, the starting materials previously investigated by
Wang and Taniguchi groups as precursors to react with sulfinic
acid or sodium sulfinate.4a,b However, sulfonehydrazide was
never used as a source of sulfonates in those reactions. We first
tested the reaction between p-toluenesulfonyl hydrazide with
phenylacetylene catalyzed by the same Cu/Fe system under
standard conditions depicted above. Interestingly, the vinyl
sulfone product 3a was isolated again in 75% yield (Table 3).
Likewise, co-catalyst FeCl2·4H2O was indispensable for this
reaction, only 55% of 3a was obatined when the additive was
absent. Several substituted aryl alkynes were also examined
under the same reaction conditions, and the results showed that
all reactions proceeded smoothly affording the corresponding
D
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Scheme 2. A Plausible Catalytic Mechanism Involving the Cu/Fe Co-Catalyst
CDCl3 on 400 MHz NMR spectrometer or 300 MHz NMR
spectrometer with TMS as an internal reference. Products were
radical D could be readily accessed with the release of
molecular nitrogen.8 Next, the addition of radical D to an
active cuprate complex E,9 which is generated by the reaction of
copper acrylate and phenylpropiolic acid/phenylacetylene,
would give an intermediate F.9 Then, the protonolysis of
intermediate F with tert-butanol which was generated in the
process of the oxidation of sulfonyl hydrazide resulted in the
generation of G.10 Eventually, target product 3a is obtained
from G with the participation of a proton produced from
previous steps, by releasing the Cu(II) species to fullfill the
catalytic cycle (Scheme 2).
1
characterized by comparison of H NMR, 13C NMR, MS, and TOF-
MS data in the literature.
General Procedure for the Reaction between Phenyl-
propiolic Acids/Phenylacetylenes and Benzenesulfonyl Hydra-
zides. To a Schlenk tube equipped with a magnetic stir bar was added
phenylpropiolic acid (0.3 mmol) or phenylacetylenes (0.3 mmol),
benzenesulfonyl hydrazide (0.6 mmol), copper acrylate (20 mol %,
0.06 mmol, 12.3 mg), FeCl2·4H2O (15 mol %, 0.045 mmol, 8.9 mg),
DTBP (0.9 mmol, 164.5 uL), and DMSO (2.0 mL). The resulting
reaction mixture was kept stirring at 100 °C for 12 h. At the end of the
reaction, the reaction mixture was cooled to room temperature. After
removal of the solvent, the residue was subjected to column
chromatography on silica gel using ethyl acetate and petroleum
ether mixtures to afford the desired product in high purity.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3a).3e White solid, mp:
CONCLUSIONS
■
In summary, we have developed a new method to selectively
synthesize (E)-vinyl sulfones through a Cu/Fe co-catalyzed
sulfonylation of propiolic acid/phenylacetylene with sulfonyl
hydrazides. In this work, for the first time sulfonyl hydrazides
were applied to the preparation of a variety of vinyl sulfones in
moderate to good yields. In contrast to previous work, this
method utilizes readily available earth-abundant metal catalysts
and features simple experimental procedure and good tolerance
of substrates. Moreover, the fact that molecular carbon dioxide
and dinitrogen are the only byproducts from the reactions
makes this process a rather green synthesis. Further studies on
the application of bimetallic co-catalysis systems based on
earth-abundant metals for other organic transformations are in
progress in our laboratory.
1
118−120 °C, yield 81% (62.8 mg); H NMR (400 MHz, CDCl3) (δ,
ppm) 7.75 (d, J = 8.0 Hz, 2H), 7.57 (d, J = 15.2 Hz, 1H), 7.39 (d, J =
7.6 Hz, 2H), 7.33−7.24 (m, 5H), 6.77 (d, J = 15.6 Hz, 1H), 2.35 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 144.4, 141.9, 137.8,
132.5, 131.1, 130.0, 129.1, 128.5, 127.7, 127.6, 21.6; MS (m/z) calcd
for C15H14O2S 258.1, found 259.1 (M + H)+.
(E)-1-Methyl-4-(4-methylstyrylsulfonyl)benzene (3b).4b White
1
solid, mp: 152−154 °C, yield 60% (49.0 mg); H NMR (400 MHz,
CDCl3) (δ, ppm) 7.82 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 15.6 Hz, 1H),
7.38−7.31 (m, 4H), 7.18 (d, J = 8.0 Hz, 2H), 6.80 (d, J = 15.2 Hz,
1H), 2.42 (s, 3H), 2.36 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
(δ, ppm) 144.3, 142.0, 141.8, 137.9, 130.0, 129.8, 129.7, 128.7, 127.7,
126.4, 21.6, 21.5; MS (m/z) calcd for C16H16O2S 272.1, found 273.1
(M + H)+.
(E)-1-Methyl-4-(4-(trifluoromethyl)styrylsulfonyl)benzene (3c).11
EXPERIMENTAL SECTION
■
1
White solid, mp: 120−122 °C, yield 41% (40.1 mg); H NMR (400
General Information. All reactions were carried out under an air
atmosphere condition. Various phenylpropiolic acid and various
benzenesulfonyl hydrazide were commercial available. The copper
acrylate (95%) and ferrous chloride tetrahydrate (99.95%) were
purchased from Alfa Aesar and Aladdin, respectively. Flash column
chromatography was performed using silica gel (100−200 mesh).
Analytical thin-layer chromatography was performed using glass plates
precoated with 200−300 mesh silica gel impregnated with a
fluorescent indicator (254 nm). NMR spectra were recorded in
MHz, CDCl3) 7.84 (d, J = 8.4 Hz, 2H), 7.56−7.71 (m, 5H), 7.36 (d, J
= 8.0 Hz, 2H), 6.95 (d, J = 15.6 Hz, 1H), 2.44 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) (δ, ppm) 144.8, 139.9, 137.1, 135.8, 132.5 (t, J =
32.6 Hz), 130.3, 130.1, 128.7, 127.9 126.0 (t, J = 3.7 Hz), 123.6 (d, J =
270.7 Hz), 21.6; MS (m/z) calcd for C16H13F3O2S 326.1, found 327.1
(M + H)+.
(E)-1-Fluoro-4-(2-tosylvinyl)benzene (3d).11 White solid, mp: 96−
98 °C, yield 72% (59.7 mg); 1H NMR (400 MHz, CDCl3) 7.82 (d, J =
E
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8.4 Hz, 2H), 7.62 (d, J = 15.6 Hz, 1H), 7.51−7.44 (m, 2H), 7.34 (d, J
= 8.0 Hz, 2H), 7.07 (t, J = 8.4 Hz, 2H), 6.80 (d, J = 15.2 Hz, 1H), 2.43
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 164.3 (d, J =
251.3 Hz), 144.5, 140.6, 137.6, 130.6 (d, J = 8.6 Hz), 130.0, 128.7 (d, J
= 3.3 Hz), 127.7, 127.4 (d, J = 2.4 Hz), 116.3 (d, J = 21.9 Hz), 21.6;
MS (m/z) calcd for C15H13F3O2S 276.1, found 277.1 (M + H)+.
(E)-1-Chloro-4-(2-tosylvinyl)benzene (3e).11 White solid, mp:
129.2, 129.1, 128.6, 128.0, 127.7, 127.3, 122.6; MS (m/z) calcd for
C18H14O2S 294.1, found 295.1 (M + H)+.
(E)-1-Chloro-4-(styrylsulfonyl)benzene (3o).3g White solid, mp:
82−84 °C, yield 42% (35.1 mg); 1H NMR (400 MHz, CDCl3) 7.90−
7.86 (m, 2H), 7.69 (d, J = 15.6 Hz, 1H), 7.53−7.46 (m, 4H), 7.43−
7.36 (m, 3H), 6.85 (d, J = 15.6 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3) (δ, ppm) 143.1, 140.1, 139.2, 132.2, 131.5, 129.7, 129.2, 129.2,
128.7, 126.8; MS (m/z) calcd for C14H11ClO2S 278.0, found 279.0 (M
+ H)+.
1
149−151 °C, yield 75% (65.9 mg); H NMR (400 MHz, CDCl3)
7.82 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 15.6 Hz, 1H), 7.43−7.38 (m,
2H), 7.37−7.32 (d, J = 8.4 Hz, 4H), 6.85 (d, J = 15.6 Hz, 1H), 2.43 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 144.6, 140.4, 137.5,
137.1, 130.9, 130.0, 129.7, 129.4, 128.2, 127.8, 21.6; MS (m/z) calcd
for C15H13ClO2S 292.0, found 293.0 (M + H)+.
(E)-1-Fluoro-4-(styrylsulfonyl)benzene (3p).3g White solid, mp:
80−82 °C, yield 41% (32.3 mg); 1H NMR (400 MHz, CDCl3) 8.00−
7.94 (m, 2H), 7.68 (d, J = 15.6 Hz, 1H), 7.51−7.46 (m, 2H), 7.43−
7.36 (m, 3H), 7.25−7.18 (m, 2H), 6.86 (d, J = 15.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3) (δ, ppm) 165.6 (d, J = 254.5 Hz), 142.7,
136.8 (d, J = 3.1 Hz), 132.2, 131.4, 130.5 (d, J = 9.6 Hz), 129.1, 128.6,
127.1, 116.7 (d, J = 22.5 Hz); MS (m/z) calcd for C14H11FO2S 262.0,
found 263.0 (M + H)+.
(E)-1-Bromo-4-(2-tosylvinyl)benzene (3f).11 White solid, mp: 162−
164 °C, yield 64% (64.7 mg); 1H NMR (400 MHz, CDCl3) 7.82 (d, J
= 8.0 Hz, 2H), 7.58 (d, J = 15.6 Hz, 1H), 7.53−7.48 (m, 2H), 7.37−
7.31 (m, 4H), 6.86 (d, J = 15.2 Hz, 1H), 2.43 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) (δ, ppm) 144.6, 140.5, 137.4, 132.3, 131.4, 130.1,
128.3, 129.9, 127.8, 125.5, 21.7; MS (m/z) calcd for C15H13BrO2S
336.0, found 337.0 (M + H)+.
(E)-1-Nitro-4-(styrylsulfonyl)benzene (3q).12 White solid, mp:
1
152−154 °C, yield 42% (36.4 mg); H NMR (400 MHz, CDCl3)
8.40−8.37 (m, 2H), 8.17−8.13 (m, 2H), 7.77 (d, J = 15.2 Hz, 1H),
7.53−7.49 (m, 2H), 7.47−7.39 (m, 3H), 6.87 (d, J = 15.2 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 150.5, 146.6, 145.0,
131.9, 131.8, 129.3, 129.0, 128.9, 125.7, 124.6; MS (m/z) calcd for
C14H11NO4S 289.0, found 290.0 (M + H)+.
(E)-1-Chloro-3-(2-tosylvinyl)benzene (3g).3b White solid, mp: 90−
92 °C, yield 65% (57.1 mg); 1H NMR (400 MHz, CDCl3) 7.82 (d, J =
8.0 Hz, 2H), 7.58 (d, J = 15.6 Hz, 1H), 7.44 (s, 1H), 7.38−7.31 (m,
5H), 6.87 (d, J = 15.2 Hz, 1H), 2.44 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) (δ, ppm) 144.7, 140.2, 137.3, 135.1, 134.3, 130.9, 130.0,
130.1, 129.2, 128.1, 127.8, 126.8, 21.6; MS (m/z) calcd for
C15H13ClO2S 292.0, found 293.0 (M + H)+.
(E)-1-Methoxy-4-(styrylsulfonyl)benzene (3r).3e White solid, mp:
83−85 °C, yield 72% (59.3 mg); 1H NMR (400 MHz, CDCl3) 7.90−
7.85 (m, 2H), 7.63 (d, J = 15.2 Hz, 1H), 7.49−7.45 (m, 2H), 7.41−
7.36 (m, 3H), 7.03−6.99 (m, 2H), 6.84 (d, J = 15.6 Hz, 1H), 3.87 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 163.6, 141.4, 132.5,
132.2, 131.0, 129.9, 129.1, 128.5, 127.9, 114.6, 55.7; MS (m/z) calcd
for C15H14O3S 274.1, found 275.1 (M + H)+.
(E)-1-Chloro-2-(2-tosylvinyl)benzene (3h).3b White solid, mp:
1
103−105 °C, yield 30% (26.3 mg); H NMR (400 MHz, CDCl3)
1H NMR (400 MHz, CDCl3) 8.08 (d, J = 15.6 Hz, 1H), 7.86 (d, J =
8.4 Hz, 2H), 7.52 (dd, J = 7.6 Hz, 1.6 Hz, 1H), 7.45 (d, J = 8.0 Hz,
1H), 7.40−7.32 (m, 3H), 7.30−7.26 (m, 1H), 6.90 (d, J = 15.6 Hz,
1H), 2.46 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 144.6,
137.9, 137.3, 135.3, 131.8, 130.8, 130.4, 130.0, 128.2, 127.9, 127.2,
21.6; MS (m/z) calcd for C15H13ClO2S 292.0, found 293.0 (M + H)+.
(E)-2-(2-Tosylvinyl)naphthalene (3j).3e White solid, mp: 160−162
(E)-1-Ethyl-4-(2-tosylvinyl)benzene (3s). White solid, mp: 80−82
1
°C, yield 71% (61.0 mg); H NMR (400 MHz, CDCl3) 7.82 (d, J =
8.0 Hz, 2H), 7.63 (d, J = 15.6 Hz, 1H), 7.39 (d, J = 8.4 Hz, 2H), 7.33
(d, J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 15.6 Hz,
1H), 2.65 (q, J = 7.6 Hz, 2H), 2.42 (s, 3H), 1.22 (t, J = 7.6 Hz, 3H);
13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 148.0, 144.3, 142.1,
137.9, 130.0, 129.9, 128.7, 128.6, 127.6, 126.4, 28.8, 21.6, 15.3; HRMS
(TOF MS CI−) calculated for C17H18O2S 286.1028, found 286.1024.
(E)-2-(2-Tosylvinyl)pyridine (3t).3b White solid, mp: 84−86 °C,
1
°C, yield 66% (61.1 mg); H NMR (400 MHz, CDCl3) 7.90 (s, 1H),
7.86 (d, J = 8.4 Hz, 2H), 7.84−7.77 (m, 4H), 7.55−7.49 (m, 3H), 7.33
(d, J = 8.0 Hz, 2H), 6.96 (d, J = 15.2 Hz, 1H), 2.42 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) (δ, ppm) 144.4, 142.0, 137.8, 134.5, 133.1,
130.9, 130.0, 129.9, 129.0, 128.7, 127.8, 127.8, 127.8, 127.7, 127.0,
123.4, 21.7; MS (m/z) calcd for C19H16O2S 308.1, found 309.1 (M +
H)+.
1
yield 62% (48.2 mg); H NMR (400 MHz, CDCl3) 8.60 (d, J = 4.0
Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.73 (td, J = 7.6 Hz, 1.6 Hz, 1H),
7.62 (d, J = 15.2 Hz, 1H), 7.44 (d, J = 15.2 Hz, 1H), 7.40 (d, J = 7.6
Hz, 1H), 7.34 (d, J = 8.0 Hz, 2H), 7.31−7.27 (m, 1H), 2.43 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 151.1, 150.3, 144.6,
140.1, 137.2, 137.1, 132.1, 130.0, 127.9, 125.4, 125.0, 21.6; MS (m/z)
calcd for C14H13NO2S 259.1, found 260.1 (M + H)+.
(E)-1-tert-Butyl-4-(2-tosylvinyl)benzene (3k).11 White solid, mp:
125−127 °C, yield 72% (67.9 mg); 1H NMR (400 MHz, CDCl3) 7.82
(d, J = 8.4 Hz, 2H), 7.64 (d, J = 15.6 Hz, 1H), 7.44−7.38 (m, 4H),
7.32 (d, J = 8.4 Hz, 2H), 6.82 (d, J = 15.2 Hz, 1H), 2.42 (s, 3H), 1.30
(s, 9H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 154.9, 144.3,
141.9, 138.0, 129.9, 128.4, 129.7, 127.6, 126.6, 126.1, 35.0, 31.1, 21.6;
MS (m/z) calcd for C19H22O2S 314.1, found 315.1 (M + H)+.
(E)-4-(2-Tosylvinyl)benzonitrile (3l). White solid, mp: 125−127 °C,
1-Methyl-4-(4-(prop-1-enyl)styrylsulfonyl)benzene (3u). Yellow
1
oil, yield 56% (50.1 mg); H NMR (400 MHz, CDCl3) 7.84 (d, J =
8.0 Hz, 2H), 7.65 (d, J = 15.6 Hz, 1H), 7.41 (d, J = 8.0 Hz, 2H), 7.35
(d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 6.82 (d, J = 15.2 Hz,
1H), 2.63 (t, J = 7.6 Hz, 2H), 2.44 (s, 3H), 1.65−1.57 (m, 2H), 1.36−
1.27 (m, 4H), 0.90 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (100 MHz,
CDCl3) (δ, ppm) 146.8, 144.3, 142.1, 138.0, 129.9, 129.9, 129.2, 128.6,
127.6, 126.4, 35.8, 31.4, 30.9, 22.5, 21.6, 14.0; HRMS (TOF MS CI−)
calculated for C20H24O2S 328.1497, found 328.1498.
1
yield 53% (45.0 mg); H NMR (400 MHz, CDCl3) 7.83 (d, J = 8.0
Hz, 2H), 7.70−7.62 (m, 3H), 7.58 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.0
Hz, 2H), 6.98 (d, J = 15.6 Hz, 1H), 2.45 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) (δ, ppm) 145.0, 139.3, 136.8, 136.7, 132.8, 131.3, 130.2,
128.9, 127.9, 118.1, 114.2, 21.7; HRMS (TOF MS CI−) calculated for
C16H13NO2S 283.0667, found 283.0669.
(E)-3-(2-Tosylvinyl)pyridine (3v).13 White solid, mp: 108−110 °C,
yield 80% (62.2 mg); 1H NMR (400 MHz, CDCl3) 8.72 (s, 1H), 8.62
(d, J = 8.8 Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.80 (dt, J = 8.0 Hz, 1.6
Hz, 1H), 7.66 (d, J = 15.6 Hz, 1H), 7.39−7.32 (m, 3H), 6.98 (d, J =
15.6 Hz, 1H), 2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) (δ,
ppm) 151.7, 149.9, 144.8, 138.2, 137.1, 134.8, 130.1, 129.9, 128.4,
127.8, 123.9, 21.7; MS (m/z) calcd for C14H13NO2S 259.1, found
260.1 (M + H)+.
(E)-(2-(Phenylsulfonyl)vinyl)benzene (3m).3e White solid, mp: 67−
69 °C, yield 80% (58.6 mg); 1H NMR (400 MHz, CDCl3) 7.98−7.93
(m, 2H), 7.68 (d, J = 15.6 Hz, 1H), 7.63−7.58 (m, 1H), 7.56−7.52
(m, 2H), 7.49−7.45 (m, 2H), 7.41−7.35 (m, 3H), 6.87 (d, J = 15.6
Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) (δ, ppm) 142.5, 140.7,
133.4, 132.3, 131.3, 129.4, 129.1, 128.6, 127.6, 127.3; MS (m/z) calcd
for C14H12O2S 244.1, found 245.1 (M + H)+.
(E)-2-(Styrylsulfonyl)naphthalene (3n).3e White solid, mp: 140−
1
142 °C, yield 76% (67.1 mg); H NMR (400 MHz, CDCl3) 8.56 (s,
ASSOCIATED CONTENT
■
1H), 8.01−7.96 (m, 2H), 7.93−7.86 (m, 2H), 7.74 (d, J = 15.2 Hz,
1H), 7.68−7.60 (m, 2H), 7.50−7.46 (m, 2H), 7.42−7.35 (m, 3H),
6.92 (d, J = 15.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) (δ,
ppm) 142.6, 137.5, 135.2, 132.4, 132.3, 131.3, 129.7, 129.4, 129.3,
S
* Supporting Information
1H and 13C NMR spectra for all products. This material is
available free of charge via the Internet at http://pubs.acs.org.
F
DOI: 10.1021/acs.joc.5b00558
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
6728. (d) Fan, B.; Li, S.; Chen, H.; Lu, Z.; Liu, S. Adv. Synth. Catal.
2013, 355, 2827. (e) Xiao, Q.; Sheng, J.; Ding, Q.; Wu, J. Adv. Synth.
Catal. 2013, 355, 2321.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jcmao@suda.edu.cn
*E-mail: guzhang@jjay.cuny.edu
■
(8) (a) Li, X.; Xu, X.; Shi, X. Tetrahedron Lett. 2013, 54, 3071.
(b) Taniguchi, T.; Idota, A.; Ishibashi, H. Org. Biomol. Chem. 2011, 9,
3151. (c) Li, X.; Xu, X.; Zhou, C. Chem. Commun. 2012, 48, 12240.
(9) (a) Hu, G.; Gao, Y.; Zhao, Y. Org. Lett. 2014, 16, 4464. (b) Lee,
J.-E.; Kwon, J.; Yun, J. Chem. Commun. 2008, 733. (c) Jia, W.; Jiao, N.
Org. Lett. 2010, 12, 2000. (d) Allen, S. E.; Walvoord, R. R.; Padilla-
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the grants from the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, State
Education Ministry, the Priority Academic Program Develop-
ment of Jiangsu Higher Education Institutions, and the Key
Laboratory of Organic Synthesis of Jiangsu Province. G.Z.
acknowledges a PSC- CUNY award (no. 67312-0045) from the
City University of New York.
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DOI: 10.1021/acs.joc.5b00558
J. Org. Chem. XXXX, XXX, XXX−XXX