Electrochemical Decarboxylative Sulfonylation of Cinnamic Acids with Aromatic Sulfonylhydrazides to Vinyl Sulfones

Article abstract of DOI:10.1021/acs.joc.7b01741

A stereoselective synthesis of (E)-vinyl sulfones has been developed via electrochemical oxidative N-S bond cleavage of aromatic sulfonylhydrazides, followed by cross-coupling reactions with cinnamic acids to form the C-S bond. The protocol proceeded smoo

Full text of DOI:10.1021/acs.joc.7b01741

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Article
Electrochemical Decarboxylative Sulfonylation of Cinnamic
Acids with Aromatic Sulfonylhydrazides to Vinyl Sulfones
Yu Zhao, Yin-Long Lai, Ke-Si Du, Dian-Zhao Lin, and Jing-Mei Huang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01741 • Publication Date (Web): 30 Aug 2017
Downloaded from http://pubs.acs.org on August 30, 2017
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Electrochemical Decarboxylative Sulfonylation of
Cinnamic Acids with Aromatic Sulfonylhydrazides to
Vinyl Sulfones
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Yu Zhao, YinꢀLong Lai, KeꢀSi Du, DianꢀZhao Lin, and JingꢀMei Huang*
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School
of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou, Guangdong 510640, China
ABSTRACT: A stereoselective synthesis of (E)ꢀvinyl sulfones has been developed via
electrochemical oxidative NꢀS bond cleavage of aromatic sulfonylhydrazides, followed by
crossꢀcoupling reactions with cinnamic acids to form the CꢀS bond. The protocol proceeded
smoothly to afford (E)ꢀvinyl sulfones in good yields with wide substrate scope under metalꢀfree
and halogenꢀfree conditions.
Introduction
Vinyl sulfones are particularly valuable units in organic synthesis1 and biological chemistry.2 As
a consequence, considerable progress has been made in the development of methodologies toward
this building block.3 However, efficient methods for preparation of vinyl sulfones in terms of
selectivity, availability of starting materials, operational simplicity, and environmentally friendly
are still in demand.
Recent years, decarboxylative crossꢀcoupling reactions have attracted a great deal of interest4
and the decarboxylative coupling of cinnamic acids with sodium sulfinates have been studied by
several groups.5 Sulfonylhydrazides are readily accessible synthetic intermediates that can also be
served as sulfone sources by means of NꢀS bond cleavage.6 Notably, N2 and water are the only
byproducts during this transformation. However, methods for decarboxylative sulfonylation of
cinnamic acids with sulfonylhydrazides are quite rare.7 In 2015, I2/TBHP treated vinyl sulfones
synthesis via decarboxylative sulfonylation of cinnamic acids with sulfonylhydrazides was first
disclosed by Singh’s group.7a Later, Cai et al. demonstrated a visibleꢀlightꢀpromoted
decarboxylative sulfonylation of cinnamic acids with sulfonylhydrazides in the presence of KI.7b
Electrochemistry has been found to be a very useful mean for the synthesis of organic compounds
and has demonstrated its advantages and environmentally friendly characteristics.8 In continuation
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of our interest in the application of electrochemical methods to organic synthesis,9 herein we
report the first efficient electrochemical decarboxylative sulfonylation of cinnamic acids with
aromatic sulfonylhydrazides to afford the vinyl sulfones in good yields.
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Results and Discussion
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To start the investigation, we chose cinnamic acid 1a and pꢀtoluenesulfonylhydrazide 2a as the
model substrates. These two compounds were treated with K2CO3 in a solution of nꢀ Bu4NBF4
(0.1 M) in DMSO in a oneꢀcompartment cell with two Pt foils (1×1.5 cm2) as electrodes under a
constant current (5 mA). The desired product 3a was obtained in a yield of 38% after the reaction
proceeded at room temperature for 10 h (Table 1, entry 1). A number of bases (Table 1, entries 2−8)
were examined. And we found that 76% yield of product was obtained when tꢀBuOLi was
employed (Table 1, entry 3). It was noted that only trace of the desired product could be obtained
in the absence of base (Table 1, entry 9). Studies on the effect of solvent showed that the yield of
product decreased sharply when DMF or NMP was used (Table 1, entries 10 and 11), while other
solvents such as CH3CN and THF disfavored the reaction (Table 1, entries 12 and 13). Hence,
DMSO was the optimal solvent for this reaction. Other electrolytes, such as NH4ClO4, NaBF4,
LiClO4, KClO4 and nꢀBu4NClO4 were screened and it was found that nꢀ(Bu)4NBF4 was the most
efficient electrolyte for this electrochemical reaction (Table 1, entries 4 and 14−18), perhaps due to
a good solubility of nꢀ(Bu)4NBF4 in DMSO.10 In addition, attempts to vary the current intensity,
Table 1. Optimization of the Reaction Conditionsa
Yield(%)b
Entry
Solvent
Base
Electrolyte
1
2
DMSO
DMSO
K2CO3
Cs2CO3
nꢀBu4NBF4
nꢀBu4NBF4
38
50
3
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
tꢀBuOLi
LiOH
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
NH4ClO4
76
4
61
5
tꢀBuONa
tꢀBuOK
DIPEA
TEA
68
6
49
7
48
8
32
9
ꢀ
trace
38
10
11
12
13
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18
19[c]
20[d]
21[e]
22[f]
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
tꢀBuOLi
NMP
41
CH3CN
THF
trace
trace
54
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
NaBF4
41
LiClO4
62
KClO4
65
nꢀBu4NClO4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
nꢀBu4NBF4
58
60
45
41
0
aReaction conditions: 1a (0.3 mmol), 2a (1.0 mmol), and tꢀBuOLi (0.6 mmol) in solvent (5 mL) with 0.1
M electrolyte was electrolyzed at a constant current (5 mA) in an undivided cell at r.t., 10 h, open air.
Anode: Pt foil (1×1.5 cm2), cathode: Pt foil (1×1.5 cm2). bYields of isolated products. cThe current was 3
mA. dThe current was 10 mA. eAnode: graphite rod electrode (diameter = 0.5 cm, height = 1.8 cm). fNo
current.
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such as 3 mA or 10 mA led to a decrease of the product yield (Table 1, entries 19 and 20).
Switching the Pt foils with graphite electrodes resulted in a yield of 41% only (Table 1, entry 21).
Finally, it was found that no reaction occurred with starting materials recovered when the reaction
was performed in the absence of current (Table 1, entry 22).
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With the optimized reaction conditions in hand, we proceeded to examine the substrate scope.
As presented in Table 2, the reactions of a series of α,βꢀunsaturated carboxylic acids with
pꢀtoluenesulfonylhydrazide 2a were screened and moderate to good yields of the corresponding
products were obtained. Firstly, cinnamic acids with a paraꢀ, metaꢀ, or orthoꢀ methyl substituent
on the aromatic ring (3b-d) could be converted into the desired products in good yields. Cinnamic
acids containing a methoxyl group (3e-g) underwent the reaction to give good yields. Additionally,
a wide range of halogenꢀcontaining α,βꢀunsaturated carboxylic acids were tested. The results
showed that halogen could be well tolerated under the electrochemical conditions (3h- k) and
could thus provide a great opportunity for further transformation at the halide position. Strong
electronꢀ withdrawing groups such as trifluoromethyl (3l) and cyano (3m) had influence on the
reaction and delivered lower yields. The reaction of 1m was run at 3 mA and was stopped at 4 h to
minimize the reduction of the cyano group on the cathode. Moreover, heteroareneꢀbased acrylic
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Table 2. Substrate Scope of α,β-Unsaturated Carboxylic Acids for Electrochemical Synthesis of 3a-qa, b
aReaction conditions: 1 (0.3 mmol), 2a (1.0 mmol), DMSO (5 mL), tꢀBuOLi (0.6 mmol), 0.1 M nꢀBu4NBF4 as
supporting electrolyte, 10 h at room temperature, anode: Pt foil (1×1.5 cm2), cathode: Pt foil (1×1.5 cm2),
constant current (5 mA), undivided cell, open air. Yield of isolated products. bConstant current (3 mA), t = 4 h.
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acids were good substrates for this process and afforded the desired product in moderate to good
yields (3n-p). It was noteworthy that the cinnamic acid with a naphthyl group (3q) was also
accommodated in the reaction and gave the desired product in a yield of 80%. In addition,
2ꢀphenylacrylic acid and crotonic acid were examined in this reaction and no desired product were
detected. Phenylpropiolic acid give a trace amount of the desired product.
To further examine the scope of this reaction, a range of sulfonylhydrazides were exposed to the
optimal reaction conditions to react with the cinnamic acids 1a. As shown in Table 3, cinnamic
acids underwent decarboxylative sulfonylation with benzenesulfonohydrazide (4a) smoothly to
afford the desired product in a yield of 70%. A series of sulfonylhydrazides with both the
electronꢀdonating (4b, 4c and 4k) and electronꢀwithdrawing (4d-h and 4l) nature of the
substituents on the aromatic ring were good partners with cinnamic acids, and the corresponding
products were obtained in moderate to good yields. Moreover, sulfonylhydrazides with a naphthyl
group or a thienyl group also participated in this reaction, and the desired products were afforded
in yields of 61% and 65%, respectively (4i and 4j). While aliphatic sulfonylhydrazide was not
compatible with the reaction conditions and no desired products was detected. It was noteworthy
that excellent E selectivity (E/Z>99:1) were observed in all product.
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Table 3. Substrate Scope of Sulfonylhydrazides for Electrochemical Synthesis of 4a-ja
aReaction conditions: 1a (0.3 mmol), 2 (1.0 mmol), DMSO (5 mL), tꢀBuOLi (0.6 mmol), 0.1 M nꢀBu4NBF4
as supporting electrolyte, 10 h at room temperature, anode: Pt foil (1×1.5 cm2), cathode: Pt foil (1×1.5 cm2),
constant current (5 mA), undivided cell, open air. Yield of isolated products..
In order to gain some insights into the reaction mechanism, a series of control experiments were
examined (Scheme 1). First, the reaction was inhibited with the addition of radical inhibitors such
as 2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy (TEMPO) and 2,6ꢀdiꢀtertꢀbutylꢀ4ꢀmethylphenol (BHT)
(Scheme 1, eq 1) under the standard conditions, suggesting the reaction presumably involved a
radical pathway. Styrene was employed as the coupling partner under the standard reaction
conditions and it was demonstrated that styrene was not the active intermediate of this reaction
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(Scheme 1, eq 2). During the process of optimization of the reaction conditions, pꢀtolylꢀdisulfide
(4) was detected. But when disulfide 4 was subjected to the reaction with 1a under the standard
conditions, no desired product was obtained. Thus, the involvement of pꢀtolyl disulfide (4) as an
intermediate for this reaction was ruled out (Scheme 1, eq 3). In addition, the yield was 69% when
the reaction was performed under an O2 atmosphere, while the yield dropped to 53% under a N2
atmosphere (Scheme 1, eq 4). Hence, air is the best atmosphere for the reaction. As the yield
decreased in the absence of air7b, 12 and the aromatic sulfonylhydazide was completely recovered
without current (Table 1, entry 22), it was proposed that the aromatic sulfonylhydazide is oxidated
by the synergistic effect of anodic oxidation and air.
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Scheme 1. Control Experiments
Cyclic voltammetry (CV) experiments were then carried out. As shown in Figure 1, an
oxidative peak at 1.24 V vs. Ag/AgCl (in Figure 1ꢀⅠ, curve c) was detected, corresponding to the
oxidation of pꢀtoluenesulfonylhydrazide.11 When tꢀBuOLi was added to the solution of
pꢀtoluenesulfonylhydrazide, one new oxidative peak at 0.53 V vs. Ag/AgCl (in Figure 1ꢀⅠ, curve
d) was obtained, which indicated that the oxidation of pꢀtoluenesulfonylhydrazide was promoted
by the base. While the anode potential of the cinnamic acid was observed at 1.38 V vs. Ag/AgCl in
the presence of base (in Figure 1ꢀⅡ, curve f). Therefore, the CV studies had shown that
pꢀtoluenesulfonylhydrazide oxidation could occur selectively during the initiation step of the
reaction under the standard conditions.
Figure 1. Cyclic voltammograms of 0.1 M nꢀBu4NBF4 solution in DMSO, using glassy carbon electrode as working
electrode (d = 3 mm), a Pt wire as counter electrode and Ag/AgCl as a reference electrode, at a scan rate of 50 mV/s:
(a) none; (b) tꢀBuOLi (0.005 M); (c) 2a (0.005 M); (d) 2a (0.005 M) and tꢀBuOLi (0.005 M); (e) tꢀBuOLi (0.015 M);
(f) 1a (0.015 M) and tꢀBuOLi (0.015 M).
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Scheme 2. Plausible Reaction Mechanism
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7, 11, 12
On the basis of our experimental results and the precedent reports,5d,
a possible
mechanism for this reaction is proposed, as depicted in Scheme 2. Aromatic sulfonylhydazide is
deprotonated to produce anion A, and anion A is then oxidized by the synergistic effect of anodic
oxidation and air to produce a highly active radical B, followed by a further oxidation to the
radical C with the release of nitrogen in the presence of a base. Subsequently, radical C reacted
with the cinnamate D to furnish the radical species E, which is easy to be decarboxylated to afford
the vinyl sulfone F under the standard conditions.
Conclusions
In conclusion, an electrochemical decarboxylative sulfonylation of cinnamic acids with
aromatic sulfonylhydrazides to synthesize vinyl sulfones has been developed. Operating
efficiently under air and at room temperature, this protocol refrains from using transition metal
catalysts, strong oxidants and halogens. The electrochemical methodology provides a new method
for the synthesis of vinyl sulfones using a decarboxylative strategy. Further investigation into the
mechanistic details and applications of this method are underway in our laboratory.
Experimental Section
General Information. Unless otherwise noted, Solvents and reagents were commercially available and used as
received without further treatment. Dimethyl sulfoxide (DMSO，H2O≤0.5%) was purchased from Tianjing Fuyu
Chemical Reagent Co. Reactions were monitored by thinꢀlayer chromatography (TLC). 1H NMR, 13C NMR
spectra were recorded at 400 and 100 MHz, respectively. Chemical shifts of H NMR and 13C NMR spectra were
1
reported as in units of parts per million (ppm) downfield from SiMe4 (δ 0.0 ppm) and relative to the signal of
chloroformꢀd (δ 7.26 ppm for 1H NMR and δ 77.1 ppm for 13C NMR). Multiplicities were given as: s (singlet); br s
(broad singlet); d (doublet); t (triplet); q (quartet); m (multiplets), etc. The number of protons (n) for a given
resonance was indicated by nH. Highresolution mass spectra (ESI) were obtained with a LCMSꢀITꢀTOF mass
spectrometer. IR spectra were obtained as potassium bromide pellets or as liquid films between two potassium
bromide pellets with a Brucker Vector 22 spectrometer.
General procedure for Electrochemical Decarboxylative Sulfonylation of Cinnamic Acids with
Sulfonylhydrazides to Vinyl Sulfones: In a roundꢀbottomed flask (5 mL), (E)ꢀcinnamic acid (0.3 mmol),
pꢀtoluenesulfonylhydrazide (1.0 mmol) and tꢀBuOLi (0.6 mmol) were dissolved in 5 mL DMSO with nꢀBu4NBF4
(0.1 M) as an electrolyte. The reaction flask was equipped with Pt foils as anode and cathode (1.5 cm2). The
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solution was electrolyzed at a constant current (5 mA) for 10 h (6.2 F/mol) under open air at ambient temperature.
After electrolysis, the mixture was quenched by water and extracted with ethyl acetate (3×15 mL). The combined
organic layer was washed with brine (5 mL) and dried over MgSO4. Purified product was obtained after column
chromatography on silica gel using a solvent mixture of petroleum ether and ethyl acetate.
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(E)ꢀ1ꢀMethylꢀ4ꢀ(styrylsulfonyl)benzene 3a. The product 3a was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (58.8 mg, 76% yield). Analytical data for 3a was
consistent with that previously reported.7a 1H NMR (400 MHz, CDCl3) δ 7.83 (d, J = 8.1 Hz, 2H),
7.65 (d, J = 15.4 Hz, 1H), 7.47ꢀ7.45 (m, 2H), 7.39ꢀ7.32 (m, 5H), 6.86 (d, J = 15.4 Hz, 1H), 2.42 (s,
3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.4, 141.9, 137.8, 132.5, 131.1, 130.0, 129.1, 128.5,
127.7, 127.7, 21.6.
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(E)ꢀ1ꢀmethylꢀ4ꢀ((4ꢀmethylstyryl)sulfonyl)benzene 3b. The product 3b was purified with silica
gel chromatography (PE/EA=5:1) as a white solid (49.0 mg, 60% yield). Analytical data for 3b
was consistent with that previously reported. 7a 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 8.3 Hz,
2H), 7.62 (d, J = 15.4 Hz, 1H), 7.37ꢀ7.32 (m, 4H), 7.18 (d, J = 8.0 Hz, 2H), 6.80 (d, J = 15.4 Hz,
1H), 2.42 (s, 3H), 2.36 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.3, 142.0, 141.7, 138.0
130.0, 129.8, 129.7, 128.6, 127.7, 126.5, 21.6, 21.5.
(E)ꢀ1ꢀmethylꢀ2ꢀ(2ꢀtosylvinyl)benzene 3c. The product 3c was purified with silica gel
chromatography (PE/EA=5:1) as a pale yellow solid solid (55.5 mg, 68% yield). Analytical data
for 3c was consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J =
15.3 Hz, 1H), 7.80 (d, J = 8.3 Hz, 2H), 7.38 (d, J = 7.6 Hz, 1H), 7.30 (d, J = 8.1 Hz, 2H),
7.26ꢀ7.23 (m, 1H), 7.17ꢀ7.12 (m, 2H), 6.74 (d, J = 15.3 Hz, 1H), 2.40 (s, 3H), 2.39 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 144.4, 139.6, 138.1, 137.8, 131.3, 131.0, 130.8, 130.0, 128.6,
127.7, 126.8, 126.5, 21.8, 19.8.
(E)ꢀ1ꢀmethylꢀ3ꢀ(2ꢀtosylvinyl)benzene 3d. The product 3
d was purified with silica gel
chromatography (PE/EA=5:1) as a ale yellow solid (62.9 mg, 77% yield). Analytical data for 3
p
d
was consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.3 Hz,
2H), 7.64 (d, J = 15.4 Hz, 1H), 7.35 (d, J = 8.1 Hz, 2H), 7.30ꢀ7.28 (m, 3H), 7.24ꢀ7.22 (m, 1H),
6.87 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H), 2.36 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.3,
142.1, 138.8, 137.9, 132.4, 131.9, 130.0, 129.1, 128.9, 127.7, 127.4, 125.8, 21.6, 21.2.
(E)ꢀ1ꢀmethoxyꢀ4ꢀ(2ꢀtosylvinyl)benzene 3e. The product 3e was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (57.9 mg, 67% yield). Analytical data for 3e was
consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.2 Hz, 2H),
7.58 (d, J = 15.4 Hz, 1H), 7.40 (d, J = 8.7 Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), 6.87 (d, J = 8.7 Hz,
2H), 6.70 (d, J = 15.3 Hz, 1H), 3.80 (s, 3H), 2.40 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ
162.0, 144.1, 141.6, 138.1, 130.3, 129.9, 127.5, 125.0, 124.8, 114.5, 55. 4, 21.5.
(E)ꢀ1ꢀmethoxyꢀ2ꢀ(2ꢀtosylvinyl)benzene 3f. The product 3f was purified with silica gel
chromatography (PE/EA=5:1) as a colourless oil (69.1 mg, 80% yield). Analytical data for 3f was
consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.88ꢀ7.81 (m, 3H),
7.40ꢀ7.31 (m, 4H), 7.06 (d, J = 15.5 Hz, 1H), 6.96ꢀ6.90 (m, 2H), 3.86 (s, 3H), 2.41 (s, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 158.8, 144.1, 138.3, 138.0, 132.4, 130.7, 129.9, 128.3, 127.7,
121.3 120.8, 111.3, 55.5, 21.6.
(E)ꢀ1ꢀmethoxyꢀ3ꢀ(2ꢀtosylvinyl)benzene 3g. The product 3g was purified with silica gel
chromatography (PE/EA=5:1) as a colourless oil (71.7 mg, 83% yield). Analytical data for 3g was
consistent with that previously reported. 5b 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 8.3 Hz, 2H),
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7.61 (d, J = 15.4 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.29 (t, J = 7.9 Hz, 1H), 7.06 (d, J = 7.7 Hz,
1H), 6.97 (s, 2H), 6.84 (d, J = 15.4 Hz, 1H), 3.80 (s, 3H), 2.43 (s, 3H). 13C{1H}NMR (100 MHz,
CDCl3) δ 160.0, 144.5, 141.9, 137.8, 133.8, 130.1, 130.0, 128.0, 127.8, 121.2, 117.1, 113.4, 55.4,
21.7.
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(E)ꢀ1ꢀfluoroꢀ4ꢀ(2ꢀtosylvinyl)benzene 3h. The product 3h was purified with silica gel
chromatography (PE/EA=5:1) as a colourless oil (46.4 mg, 56% yield). Analytical data for 3h was
consistent with that previously reported.5c 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.3 Hz, 2H),
7.61 (d, J = 15.4 Hz, 1H), 7.48ꢀ7.44 (m, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.06 (t, J = 8.6 Hz, 2H),
6.79 (d, J = 15.4 Hz, 1H), 2.42 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 164.4 (d, JCꢀF = 251.3
Hz), 144.5, 140.6, 137.7, 130.6 (d, JCꢀF = 8.7 Hz), 130.0, 128.8 (d, JCꢀF = 3.3 Hz), 127.7, 127.5 (d,
JCꢀF = 2.3 Hz), 116.3 (d, JCꢀF = 2.2 Hz), 21.6.
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(E)ꢀ1ꢀchloroꢀ4ꢀ(2ꢀtosylvinyl)benzene 3i. The product 3i was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (73.6 mg, 84% yield). Analytical data for 3i was
consistent with that previously reported.5c 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 8.3 Hz, 2H),
7.60 (d, J = 15.4 Hz, 1H), 7.41ꢀ7.39 (m, 2H), 7.36ꢀ7.33 (m, 4H), 6.83 (d, J = 15.4 Hz, 1H), 2.43 (s,
3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.6, 140.5, 137.6, 137.2, 131.0, 130.1, 129.8, 129.4,
128.3, 127.8, 21.7.
(E)ꢀ1ꢀChloroꢀ2ꢀ(2ꢀtosylvinyl)benzene 3j. The product 3j was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (72.7 mg, 83% yield). Analytical data for 3j was
consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 15.4 Hz,
1H), 7.85 (d, J = 8.1 Hz, 2H), 7.50 (d, J = 7.7 Hz, 1H), 7.42 (d, J = 8.0 Hz, 1H), 7.37ꢀ7.24 (m, 4H),
6.91 (d, J = 15.5 Hz, 1H), 2.44 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.6, 137.8, 137.4,
135.2, 131.9, 130.8, 130.4, 130.4 130.1, 128.2, 127.9, 127.2, 21.6.
(E)ꢀ1ꢀbromoꢀ4ꢀ(2ꢀtosylvinyl)benzene 3k. The product 3k was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (66.5 mg, 66% yield). Analytical data for 3k was
consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 8.2 Hz, 2H),
7.58 (d, J = 15.4 Hz, 1H), 7.52 (d, J = 8.4 Hz, 2H), 7.35 (t, J = 7.5 Hz, 4H), 6.84 (d, J = 15.4 Hz,
1H), 2.44 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.7, 140. 6, 137.6, 132.4, 131.5, 130.1,
129.9, 128.5, 127. 9, 125.6, 21.7.
(E)ꢀ1ꢀmethylꢀ4ꢀ((4ꢀ(trifluoromethyl)styryl)sulfonyl)benzene 3l. The product 3l was purified
with silica gel chromatography (PE/EA=5:1) as a white solid (51.8 mg, 53% yield). Analytical
data for 3l was consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.83 (d, J
= 8.2 Hz, 2H), 7.68ꢀ7.61 (m, 3H), 7.57 (d, J = 8.3 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 6.97 (d, J =
15.4 Hz, 1H), 2.42 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.8, 139.9, 137.2, 135.9, 132.5
(q, JCꢀF = 32.6 Hz), 130.5, 130.1, 128.7, 127.9, 126.0 (q, JCꢀF = 3.7 Hz), 123.7(q, JCꢀF = 270.8 Hz),
21.5.
(E)ꢀ4ꢀ(2ꢀTosylvinyl)benzonitrile 3m. The product 3m was purified with silica gel
chromatography (PE/EA=5:1) as a yellow solid (25.5 mg, 30% yield). Analytical data for 3m was
consistent with that previously reported. 7a 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 8.1 Hz, 2H),
7.69ꢀ7.55 (m, 5H), 7.36 (d, J = 8.1 Hz, 2H), 6.95 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H). 13C{1H}NMR
(100 MHz, CDCl3) δ 145.1, 139.3, 137.0, 136.8, 132.8, 131.5, 130.2, 128.9, 128.0, 118.1, 114.3,
21.7.
(E)ꢀ2ꢀ(2ꢀtosylvinyl)furan 3n. The product 3n was purified with silica gel chromatography
(PE/EA=5:1) as a white solid (51.3 mg, 69% yield). Analytical data for 3n was consistent with
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that previously reported. 3g 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 8.3 Hz, 2H), 7.46 (s, 1H),
7.40 (d, J = 15.1 Hz, 1H), 7.32 (d, J = 8.1 Hz, 2H), 6.72 (d, J = 15.1 Hz, 1H), 6.68 (s, 1H), 6.46 (s,
1H), 2.41 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 148.8, 145.6, 144.3, 138.0, 130.0, 128.5,
127.6, 125.2, 116.7, 112.6, 21.6.
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(E)ꢀ2ꢀ(2ꢀtosylvinyl)thiophene 3o. The product 3o was purified with silica gel chromatography
(PE/EA=5:1) as a brown solid (52.3 mg, 66% yield). Analytical data for 3o was consistent with
that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.1 Hz, 2H), 7.75 (d, J =
15.1 Hz, 1H), 7.41 (d, J = 4.9 Hz, 1H), 7.33 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 3.4 Hz, 1H),
7.10ꢀ7.01 (m, 1H), 6.63 (d, J = 15.1 Hz, 1H), 2.42 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ
144.4, 137.9, 137.1, 134.6, 132.3, 130.0, 129.9, 128.3, 127.7, 125.9, 21.6.
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(E)ꢀ2ꢀ(2ꢀtosylvinyl)pyridine 3p. The product 3p was purified with silica gel chromatography
(PE/EA=5:1) as a yellow oil (58.3 mg, 75% yield). Analytical data for 3p was consistent with that
previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 8.59 (d, J = 4.7 Hz, 1H), 7.83 (d, J = 8.3 Hz,
2H), 7.74ꢀ7.70 (m, 1H), 7.61 (d, J = 14.9 Hz, 1H), 7.42 (m, 2H), 7.33 (d, J = 8.0 Hz, 2H),
7.29ꢀ7.26 (m, 1H), 2.42 (s, 3H). 13C{1H}NMR (100MHz, CDCl3) δ 151.1, 150.3, 144.6, 140.1,
137.3, 137.1, 132.2, 130.0, 127.9, 125.4, 125.0, 21.6.
(E)ꢀ2ꢀ(2ꢀtosylvinyl)naphthalene 3q. The product 3q was purified with silica gel
chromatography (PE/EA=5:1) as a yellow solid (73.9 mg, 80% yield). Analytical data for 3q was
consistent with that previously reported. 3p 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 17.7 Hz,
2H), 7.86ꢀ7.80 (m, 5H), 7.55ꢀ7.51 (m, 3H), 7.35 (d, J = 7.9 Hz, 2H), 6.96 (d, J = 15.4 Hz, 1H),
2.43 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.5, 142.1, 137.9, 134.5, 133.2, 130.9, 130.0,
130.0, 129.0, 128.7, 127.9, 127.8, 127.7, 127.0, 123.5, 21.7.
(E)ꢀ(2ꢀ(phenylsulfonyl)vinyl)benzene 4a. The product 4a was purified with silica gel
chromatography (PE/EA=5:1) as a pale yellow solid (51.3 mg, 70% yield). Analytical data for 4a
was consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.4 Hz,
2H), 7.69 (d, J = 15.4 Hz, 1H), 7.63ꢀ7.59 (m, 1H), 7.54 (t, J = 7.6 Hz, 2H), 7.48ꢀ7.46 (m, 2H),
7.38 (d, J = 6.7 Hz, 3H), 6.87 (d, J = 15.4 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 142.5,
140.8, 133.4, 132.4, 131.3, 129.4, 129.1, 128.6, 127.7, 127.3.
(E)ꢀ1ꢀtertꢀbutylꢀ4ꢀ(styrylsulfonyl)benzene 4b. The product 4b was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (52.2 mg, 58% yield). Analytical data for 4b was
consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 7.7 Hz, 2H),
7.67 (d, J = 15.4 Hz, 1H), 7.55 (d, J = 7.7 Hz, 2H), 7.47 (d, J = 7.1 Hz, 2H), 7.38 (d, J = 6.0 Hz,
3H), 6.87 (d, J = 15.4 Hz, 1H), 1.33 (s, 9H). 13C{1H}NMR (100 MHz, CDCl3) δ 157.4, 142.0,
137.7, 132.5, 131.1, 129.1, 128.6, 127.6, 127.6, 126.4, 35.3, 31.1.
(E)ꢀ1ꢀmethoxyꢀ4ꢀ(styrylsulfonyl)benzene 4c. The product 4c was purified with silica gel
chromatography (PE/EA=5:1) as a white oil (66.6 mg, 81% yield). Analytical data for 4c was
consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.8 Hz, 2H),
7.62 (d, J = 15.4 Hz, 1H), 7.46ꢀ7.44 (m, 2H), 7.36 (d, J = 6.4 Hz, 3H), 6.99 (d, J = 8.7 Hz, 2H),
6.85 (d, J = 15.4 Hz, 1H), 3.84 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 163.6, 141.3, 132.5,
132.2 131.0, 129.8, 129.0, 128.5, 128.0, 114.6, 55.7.
(E)ꢀ1ꢀfluoroꢀ4ꢀ(styrylsulfonyl)benzene 4d. The product 4d was purified with silica gel
chromatography (PE/EA=5:1) as a pale yellow solid (47.2 mg, 60% yield). Analytical data for 4d
was consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 7.98ꢀ7.94 (m, 2H),
7.68 (d, J = 15.4 Hz, 1H), 7.49ꢀ7.47 (m, 2H), 7.43ꢀ7.37 (m, 3H), 7.23ꢀ7.19 (m, 2H), 6.85 (d, J =
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15.4 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 165.7(d, JCꢀF = 254.4 Hz), 142.7, 136.8 (d, JCꢀF
= 3.1 Hz), 132.2, 131.4, 130.6 (d, JCꢀF = 9.5 Hz), 129.2, 128.6, 127.1, 116.7(d, JCꢀF = 22.5 Hz).
(E)ꢀ1ꢀchloroꢀ4ꢀ(styrylsulfonyl)benzene 4e. The product 4e was purified with silica gel
chromatography (PE/EA=5:1) as a brown solid (65.9 mg, 79% yield). Analytical data for 4e was
consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.6 Hz, 2H),
7.58 (d, J = 15.4 Hz, 1H), 7.41ꢀ7.36 (m, 4H), 7.31ꢀ7.26 (m, 3H), 6.77 (d, J = 15.4 Hz, 1H).
13C{1H}NMR (100 MHz, CDCl3) δ 143.0, 140.0, 139.3, 132.1, 131.4, 129.6, 129.1, 129.1, 128.6,
126.9.
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(E)ꢀ1ꢀbromoꢀ4ꢀ(styrylsulfonyl)benzene 4f. The product 4f was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (60.9 mg, 63% yield). Analytical data for 4f was
consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.3 Hz, 2H),
7.70ꢀ7.67(m, 3H), 7.48 (d, J = 6.8 Hz, 2H), 7.42ꢀ7.39 (m, 3H), 6.84 (d, J = 15.4 Hz, 1H).
13C{1H}NMR (100 MHz, CDCl3) δ 143.2, 139.9, 132.7, 132.2, 131.5, 129.3, 129.2, 128.7, 126.9.
(E)ꢀNꢀ(4ꢀ(styrylsulfonyl)phenyl)acetamide 4g. The product 4g was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (38.8 mg, 43% yield). Analytical data for 4g was
consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H), 7.83 (d, J =
8.5 Hz, 2H), 7.71 (d, J = 8.5 Hz, 2H), 7.63 (d, J = 15.4 Hz, 1H), 7.46 (d, J = 6.2 Hz, 2H), 7.38 (d,
J = 7.0 Hz, 3H), 6.84 (d, J = 15.4 Hz, 1H), 2.19 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 169.5,
143.2, 142.3, 134.7, 132.2, 131.3, 129.1, 128.8, 128.6, 127.2, 119.8, 24.6.
(E)ꢀ1ꢀ(styrylsulfonyl)ꢀ4ꢀ(trifluoromethyl)benzene 4h. The product 4h was purified with silica
gel chromatography (PE/EA=5:1) as a pale yellow solid (47.7 mg, 51% yield). Analytical data for
4h was consistent with that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.3
Hz, 2H), 7.80 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 15.4 Hz, 1H), 7.50ꢀ7.48 (m, 2H), 7.43ꢀ7.38 (m, 3H),
6.88 (d, J = 15.4 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 144.5, 144.1, 135.0 (q, JCꢀF = 32.9
Hz), 132.1, 131.7, 129.2, 128.8, 128.3, 126.5 (q, JCꢀF = 3.7 Hz), 126.3, 123.2(q, JCꢀF = 271.4 Hz).
(E)ꢀ2ꢀ(styrylsulfonyl)thiophene 4i. The product 4i was purified with silica gel chromatography
(PE/EA=5:1) as a yellow solid (45.8 mg, 61% yield). Analytical data for 4i was consistent with
that previously reported. 7b 1H NMR (400 MHz, CDCl3) δ 7.72ꢀ7.66 (m, 3H), 7.49 (d, J = 7.7 Hz,
2H), 7.42ꢀ7.39 (m, 3H), 7.15ꢀ7.13 (m, 1H), 6.96 (d, J = 15.3 Hz, 1H). 13C{1H}NMR (100 MHz,
CDCl3) δ 142.3, 142.2, 134.0, 133.5, 132.3, 131.4, 129.2, 128.7, 128.1, 128.0.
(E)ꢀ2ꢀ(styrylsulfonyl)naphthalene 4j. The product 4j was purified with silica gel
chromatography (PE/EA=5:1) as a white solid (457.3 mg, 65% yield). Analytical data for 4j was
consistent with that previously reported.3e 1H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 7.99ꢀ7.96
(m, 2H), 7.91ꢀ7.88 (m, 2H), 7.75 (d, J = 15.4 Hz, 1H), 7.67ꢀ7.59 (m, 2H), 7.49ꢀ7.47 (m, 2H),
7.40ꢀ7.37 (m, 3H), 6.94 (d, J = 15.4 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 142.6, 137.6,
135.2, 132.4, 132.3, 131.3, 129.7, 129.4, 129.3, 129.2, 129.1, 128.6, 128.0, 127.7, 127.4, 122.6.
(E)ꢀ1ꢀmethoxyꢀ2ꢀ(styrylsulfonyl)benzene 4k. The product 4k was purified with silica gel
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chromatography (PE/EA=5:1) as a yellow oil (59.2 mg, 72% yield). H NMR (400 MHz, CDCl3)
δ 8.02 (d, J = 7.6 Hz, 1H), 7.69 (d, J = 15.5 Hz, 1H), 7.56 (t, J = 8.4 Hz, 1H), 7.50ꢀ7.48 (m, 2H),
7.40ꢀ 7.38 (m, 3H), 7.15ꢀ7.09 (m, 2H), 7.01 (d, J = 8.3 Hz, 1H), 3.96 (s, 3H). 13C{1H}NMR (100
MHz, CDCl3) δ 157.4, 143.3, 135.4, 132.9, 131.0, 129.5, 129.1, 128.7, 128.5, 127.0, 120.8, 112.5,
56.3. IR (KBr): 3060, 2926, 2846, 1585, 1471, 1297, 1137, 1013, 812, 748 cmꢀ1
calculated for C15H14NaO3S (M + Na+): 297.0556, found:297.0559.
. HRMS
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(E)ꢀ1ꢀchloroꢀ2ꢀ(styrylsulfonyl)benzene 4l. The product 4l was purified with silica gel
chromatography (PE/EA=5:1) as a pale yellow solid (57.6 mg, 69% yield). Analytical data for 4l
was consistent with that previously reported. 5a 1H NMR (400 MHz, CDCl3) δ 8.22 (d, J = 7.9 Hz,
1H), 7.77 (d, J = 15.4 Hz, 1H), 7.54ꢀ7.38 (m, 8H), 7.08 (d, J = 15.4 Hz, 1H). 13C{1H}NMR (100
MHz, CDCl3) δ 145.3, 138.3, 134.6, 132.9, 132.4, 131.9, 131.5, 130.7, 129.2, 128.8, 127.5,
125.37.
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ASSOCIATED CONTENT
Supporting Information
Experimental spectroscopic data. This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: chehjm@scut.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful to the National Natural Science Foundation of China (Grant Nos. 21372089 and
21672074) for financial support.
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