Copper-catalyzed aerobic decarboxylative sulfonylation of cinnamic acids with sodium sulfinates: Stereospecific synthesis of (E)-alkenyl sulfones

Article abstract of DOI:10.1021/jo5010845

A copper-catalyzed aerobic decarboxylative sulfonylation of alkenyl carboxylic acids with sodium sulfinates is developed. This study offers a new and expedient strategy for stereoselective synthesis of (E)-alkenyl sulfones that are widely present in biolo

Full text of DOI:10.1021/jo5010845

Article
pubs.acs.org/joc
Copper-Catalyzed Aerobic Decarboxylative Sulfonylation of
Cinnamic Acids with Sodium Sulfinates: Stereospecific Synthesis of
(E)‑Alkenyl Sulfones
Qing Jiang, Bin Xu, Jing Jia, An Zhao, Yu-Rou Zhao, Ying-Ying Li, Na-Na He, and Can-Cheng Guo*
State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of
Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China
S
* Supporting Information
ABSTRACT: A copper-catalyzed aerobic decarboxylative sulfonyla-
tion of alkenyl carboxylic acids with sodium sulfinates is developed.
This study offers a new and expedient strategy for stereoselective
synthesis of (E)-alkenyl sulfones that are widely present in biologically
active natural products and therapeutic agents. Moreover, the
transformation is proposed to proceed via a radical process and
exhibits a broad substrate scope and good functional group tolerance.
catalyzed decarboxylative sulfonylation of alkenyl carboxylic
acids with sodium sulfinates using air as the oxidant. The
significance of the present chemistry is 3-fold: (1) this is the
first aerobic decarboxylative sulfonylation of alkenyl carboxylic
acids utilizing sodium sulfinates as the sulfur source without any
silver additives for stereoselective synthesis of (E)-alkenyl
sulfones, a structural motif considered to be both a useful
synthetic intermediate9 and a privileged medicinal target.10
Although many synthetic methods have been developed for the
preparation of vinyl sulfones, limitations, including the use of
expensive or toxic reagents, narrow substrate scope, preinstalled
functional groups, poor functional group tolerance, and
multistep processes, restrict the applications of these method-
ologies.11,12 (2) Inexpensive copper salt is employed as the
catalyst, and molecular oxygen is used as a green oxidant and
plays a very important role to initiate this transformation, which
makes this protocol very easily handled. (3) The mechanistic
study indicates that the initial sulfonyl cation addition and the
following decarboxylation processes are involved in this
transformation.
INTRODUCTION
■
Transition-metal-catalyzed C−C and C−heteroatom bond-
forming reactions are among the most powerful methods in
modern synthetic chemistry and play a crucial role in fine
chemicals, material science, and medicinal chemistry.1 Among
them, decarboxylative couplings2 catalyzed by transition metals
have proven to be one of the most powerful and versatile
processes for the formation of C−C,3 C−N,4 C−S,5 and C−P6
bonds due to the “neutral ” conditions, the readily available
starting materials, and the nontoxic byproduct (CO2). Notably,
Pd catalysts have been shown to be extraordinarily versatile for
decarboxylative coupling since the pioneering work of Myers
and Goossen. However, those palladium-catalyzed methods
suffer from some drawbacks: (1) palladium is quite expensive;
(2) other additives, such as stoichiometric silver salts, are
frequently encountered in the reactions; and (3) air- or
moisture-sensitive, and very expensive, bulky phosphine ligands
are always required for the success of the reactions. From a
synthetic perspective, the development of analogous reactions
using inexpensive metals such as copper and iron would be of
significant importance. In this context, the copper-catalyzed
decarboxylative coupling reactions have drawn considerable
attention in recent years because of their low cost,
commercially availability, and environmentally friendly charac-
ter.7 In this regard, different coupling partners, such as
benzothiazoles,7a dialkyl H-phosphonates,6a,b amines,4a−c am-
monia,4e thiols,5a sodium trifluoromethanesulfinate,7b and
alkanes,7c,i have been employed to couple with carboxylic
acids to provide higher functionalized molecules. During our
investigation on mechanistic study and the process of
preparation of this paper, Liu reported a copper/silver-
mediated construction of 2-sulfonylbenzo[b]furans from
trans-2-hydroxycinnamic acids and sodium sulfinates via a
protodecarboxylation/sulfonylation/cyclization cascade.5b This
prompted us to report our findings. As part of our continuing
interest in C−C cleavage reactions,8 we herein report a Cu(II)-
RESULTS AND DISCUSSION
■
We initiated our studies with the screening of the conditions for
the decarboxylative coupling of cinnamic acid 1a and sodium
benzenesulfinate 2a. It was found that, while a clean coupling
occurred under an air atmosphere when CuO (20 mol %) was
utilized as a catalyst, the desired product 3a was isolated in only
38% yield due to low conversion (Table 1, entry 1). The yield
of isolated 3a was dramatically improved to 74% when KI as an
additive was added to the reaction mixture (Table 1, entry 2).
Addition of other additives including NaI, KBr, and AcOH
failed to give any positive effect (Table 1, entries 3−6). Further
Received: May 17, 2014
© XXXX American Chemical Society
A
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a
sulfinate substrate was explored in the coupling with cinnamic
acid. Sodium benzenesulfinate bearing electron-donating and
electron-withdrawing groups in the benzene ring, such as
sodium 4-toluenesulfinate and sodium 4-chlorobenzenesulfi-
nate, furnished 3p and 3q in 56% and 64% yield, respectively
(entries 16 and 17). In addition, sodium methanesulfinate, a
aliphatic sodium sulfinate, was also a viable partner, affording
the vinyl sulfone 3r in 33% yield (entry 18).
Table 1. Optimization of the Reaction Conditions
b
entry
catalyst (mol %)
additive
solvent
yield (%)
1
2
CuO (20)
CuO (20)
CuO (20)
CuO (20)
CuO (20)
CuO (20)
CuCl2 (20)
CuCl (20)
CuBr2 (20)
CuI (20)
none
KI
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
38
74
57
24
trace
28
23
37
14
54
53
12
42
60
20
9
Though the exact mechanism of this coupling is still not
clear, some information has been gathered. When radical
inhibitors, such as 2,2,6,6-tetramethyl-1-piperidinyloxy
(TEMPO), hydroquinone, and 2,6-di-tert-butyl-4-methylphenol
(BHT), were employed in the standard reaction, the reaction
was obviously inhibited (Scheme 1a). The results implied that
the reaction presumably underwent a radical pathway. When
methyl cinnamate 4 was reacted with 2a with and without a
stoichiometric amount of AcOH (1.5 equiv) under the standard
reaction conditions, the product 5 was not observed and almost
all of the methyl cinnamate 4 remained intact (Scheme 1b).
This result suggested that the carboxyl group is essential for the
reaction to proceed efficiently. Moreover, no reaction occurred
as determined by HPLC when only cinnamic acid was
subjected to the standard reaction conditions (Scheme 1c).
The reaction failed to give the desired product 3a when 2a was
treated with styrene under the standard conditions, whereas,
when this reaction was performed in the presence of AcOH
under otherwise identical conditions, under the conditions that
are similar to that developed by Taniguchi,12a the desired
product 3a was obtained in 18% yield (Scheme 1d). When the
trans-2-hydroxy-cinnamic acid, which is a substrate studied in Li
and Liu’s work,5b was conducted under the standard conditions,
the vinyl sulfone 3s was obtained in 32% yield and no
cyclization product 6 was observed (Scheme 1e). The above
results indicated that the initial protodecarboxylation and the
following sulfonylation processes might not be involved in the
reaction mechanism.
On the basis of these results, a plausible mechanism is
proposed and shown in Scheme 2 (using cinnamic acid and
sodium benzenesulfinate as the model). Under the reaction
conditions, benzenesulfinyl anion is first oxidized by Cu(II), air,
or DMSO by single electron transfer (SET) to induce the
formation of an oxygen-centered radical A resonating with
sulfonyl radical B.12a,13 Through further single electron
oxidation, this carbon radical B would be converted to
intermediate cation C.5b Subsequently, the addition of C to
the α-position of the double bond in cupric cinnamate D,7c
which is generated by the reaction of cinnamic acid 1a with
cupric oxide, would give an intermediate E, followed by
trapping by the iodide ion to afford F. The validity of reaction
intermediate E can be supported by the reaction results of
nitro-substituted cinnamic acids (entries 5−7, Table 2). Among
them, the pKa of the ortho/para-nitro benzyl position would be
significantly lower than the meta-nitro due to resonance.
Therefore, the stability of the benzyl cation (species E) should
have an inverse stability to the anion. In this case, the
experimental results call the formation of cation E into question
since the ortho-nitro cinnamic acid gives the highest yield, and
to stabilize the benzyl cation, one of the resonance structures
puts the cation onto the carbon attached to the nitro
substituent. Therefore, an argument could be made that, even
though the ortho- and para-nitro benzyl cations are difficult to
form, they react much more quickly with the iodide if at all
formed. Moreover, the result obtained from entry 2 in Table 1
3
NaI
NH4I
KBr
AcOH
KI
4
5
6
7
8
KI
9
KI
10
11
12
KI
Cu(AcO)2 (20)
FeCl3 (20)
CuO (20)
CuO (20)
CuO (20)
CuO (20)
CuO (20)
none
KI
KI
c
13
KI
d
14
KI
15
16
17
18
KI
KI
DCE
KI
CH3CN
DMSO
DMSO
DMSO
4
KI
trace
trace
56
e
19
CuO (20)
CuO (5)
KI
20
KI
a
Reactions conditions: 1a (0.5 mmol), 2a (1.5 mmol), catalyst,
additive (1.5 equiv), solvent (2 mL), 100 °C, 24 h, sealed tube under
b
c
d
e
air. Isolated yield. 80 °C. 110 °C. Under N2.
screening of different catalysts gave CuO as the best choice
(Table 1, entries 7−12). Lowering or elevating the reaction
temperature all gave rise to a much lower yield (Table 1, entries
13 and 14). A screening of solvents revealed that DMSO was
optimal (Table 1, entries 15−17). Control experiments
indicated that only a trace amount of 3a was detected by
HPLC in the absence of the catalyst (Table 1, entry 18), and air
was necessary for the reaction to proceed (Table 1, entry 19).
In addition, when the catalyst loading was reduced to 5 mol %,
under which conditions product 3a was isolated in 56% yield
(Table 1, entry 20). Thus, the optimal conditions constitute a
combination of CuO (20 mol %) and KI (1.5 equiv) in DMSO
at 100 °C under an air atmosphere for 24 h.
With the optimized protocol in hand, the scope and
limitation of this decarboxylation system were next explored.
Cinnamic acids in reaction with 2a was examined first (Table
2). The reaction worked very well for a range of cinnamic acids
with various substituents at the phenyl ring, and the products
were isolated in yields ranging from 34% to 85%. Cinnamic acid
derivatives with electron-donating substituents at the phenyl
ring afforded the desired vinyl sulfones in 34−54% yield
(entries 2−4), whereas cinnamic acid derivatives bearing
electron-withdrawing substituents at the phenyl ring provided
the desired vinyl sulfones in 66−85% yield (entries 5−10). The
experimental results indicated that para-, meta-, and ortho-nitro
substituted cinnamic acid afforded similar yields (entries 5−7,
66−72% yield). Sterically hindered α-methylcinnamic acid was
not suitable for this transformation (entry 11, 0% yield).
Moreover, the arene ring is not limited to benzene rings.
Pyridines, furans, and thiophenes also coupled with cinnamic
acid, thus providing the corresponding desired products in 57−
67% yield (entries 12−15). Finally, the scope of the sodium
B
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Table 2. Substrate Scope of the Aerobic Decarboxylative Sulfonylation of a Variety of Alkenyl Carboxylic Acids with Various
a b c
, ,
Sodium Sulfinates
a
Reaction conditions: cinnamic acids (0.5 mmol), sodium sulfinates (1.5 mmol), CuO (20 mol %), KI (1.5 equiv), DMSO (2 mL), 100 °C, 24 h,
b
c
sealed tube under air. Sodium methanesulfinate (3.0 mmol). The cited yields are of material isolated by column chromatography.
may also indicate that the Michael acceptor is undergoing
conjugate addition with the iodide, thereby eliminating cation E
as a reactive intermediate at least in the case of the nitrophenyl
analogues. Finally, the F would undergo the anti elimination of
Cu(I)I and carbon dioxide to afford the desired product 3a. In
addition, a direct pathway leading from E to 3a is also likely.7c
Then, the Cu(I) is reoxidized to Cu(II) by air, thus completing
the catalytic cycle. However, it is very unlikely that these
reaction conditions could induce such a high energy species as a
phenyl radical, which would inhabit an electron-deficient orbital
orthogonal to a node of the aromatic system because cinnamic
acid derivatives with electron-withdrawing substituents at the
phenyl ring provided the desired vinyl sulfones in good yields
(entries 5−10, Table 2).
sodium sulfinates has been developed using air as the oxidant. A
wide range of cinnamic acid and sodium sulfinate substrates
undergo decarboxylative coupling to produce the correspond-
ing sulfonylation products in moderate to good yields.
Preliminary mechanistic studies suggested that this reaction is
likely to proceed through a radical pathway. This new and
expedient synthetic protocol for vinyl sulfones may have wide
applications to the industrial process in the future.
EXPERIMENTAL SECTION
■
General Comments. All reagents and solvents used were obtained
commercially and used without further purification unless indicated
otherwise. All products were characterized by 1H NMR and 13C NMR.
1H NMR spectra were recorded on 400 MHz in CDCl3 or DMSO-d6,
and 13C NMR spectra were recorded on 101 MHz in CDCl3 or
DMSO-d6 using TMS as internal standard. Multiplicities are indicated
as s (singlet), d (doublet), t (triplet), q (quartet), and m (multiplet),
CONCLUSIONS
■
1
In summary, the first copper-catalyzed stereoselective decar-
boxylative C−S coupling reaction of cinnamic acids with
and coupling constants (J) are reported in hertz. Copies of H NMR
and 13C NMR spectra are provided as the Supporting Information.
C
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Scheme 1. Control Experiments
air. The reaction mixture was then allowed to cool to room
temperature, after which the crude reaction mixture was loaded
directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (90.3 mg, 74%). Flash
chromatography (petroleum ether/ethyl acetate, 10/1); colorless oil;
1H NMR (CDCl3, 400 MHz) δ 6.87 (d, J = 16.0 Hz, 1 H), 7.39−7.42
(m, 3 H), 7.47−7.50 (m, 2 H), 7.55 (t, J = 8.0 Hz, 2 H), 7.60−7.64
(m, 1 H), 7.69 (d, J = 16.0 Hz, 1 H), 7.95 (d, J = 8.0 Hz, 1 H); 13C
NMR (CDCl3, 101 MHz) δ 127.2, 127.6, 128.6, 129.1, 129.3, 131.2,
132.7, 133.4, 140.6, 142.5 ppm; LRMS: m/z calcd for C13H17NO2 (M
+ H): 244, found: 244.
Scheme 2. Proposed Reaction Mechanism
(E)-1-Methyl-4-(2-(phenylsulfonyl)vinyl)benzene (3b). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), 4-methylcinnamic acid (81 mg, 0.5 mmol,
1 equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (69.7 mg, 54%). Flash
chromatography (petroleum ether/ethyl acetate, 5/1); colorless solid,
mp = 134.1−136.3 °C; 1H NMR (CDCl3, 400 MHz) δ 2.37 (s, 3 H),
6.81 (d, J = 16.0 Hz, 1 H), 7.19 (d, J = 8.0 Hz, 2 H), 7.38 (d, J = 8.0
Hz, 3 H), 7.52−7.68 (m, 4 H), 7.95 (d, J = 8.0 Hz, 2 H); 13C NMR
(CDCl3, 101 MHz) δ 21.6, 126.1, 127.6, 128.6, 129.3, 129.6, 129.8,
133.3, 140.9, 141.9, 142.6 ppm; Anal.Calcd for C15H14O2S Elemental
Analysis: C, 69.74; H, 5.46; Found: C, 69.67; H, 5.54.
Typical Procedure for the Aerobic Decarboxylative Sulfo-
nylation of Cinnamic Acids with Sodium Sulfinates Catalyzed
by Copper. A 25 mL sealed tube was charged with cinnamic acids
(0.5 mmol, 1 equiv), sodium sulfinates (1.5 mmol, 3 equiv), CuO (0.1
mmol, 0.2 equiv), KI (0.75 mmol, 1.5 equiv), and DMSO (2 mL). The
reaction was stirred at 100 °C for 24 h in air. Upon completion of the
reaction, the reaction mixture was then allowed to cool to room
temperature, after which the crude reaction mixture was loaded
directly onto a column of silica gel and purified by column
chromatography to give the desired product (E)-alkenyl sulfones.
(E)-1-Phenylsulfonyl-2-phenylethene (3a). CuO (7.9 mg, 0.1
mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75 mmol,
1.5 equiv), cinnamic acid (74 mg, 0.5 mmol, 1 equiv), and sodium
benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in DMSO (2 mL) at
room temperature. The reaction was stirred at 100 °C for 24 h under
(E)-1-Methoxyl-4-(2-(phenylsulfonyl)vinyl)benzene (3c).
CuO (7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI
(124.5 mg, 0.75 mmol, 1.5 equiv), 4-methoxylcinnamic acid (89 mg,
0.5 mmol, 1 equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol,
3 equiv) in DMSO (2 mL) at room temperature. The reaction was
D
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stirred at 100 °C for 24 h under air. The reaction mixture was then
allowed to cool to room temperature, after which the crude reaction
mixture was loaded directly onto a column of silica gel and purified by
column chromatography to give the vinyl sulfone (57.5 mg, 42%).
Flash chromatography (petroleum ether/ethyl acetate, 2/1); yellow
oil; 1H NMR (CDCl3, 400 MHz) δ 3.83 (s, 1 H), 6.70 (d, J = 16.0 Hz,
1 H), 6.90 (d, J = 8.0 Hz, 2 H), 7.43−7.66 (m, 7 H), 7.95 (d, J = 6.8
Hz, 2 H); 13C NMR (CDCl3, 101 MHz) δ 55.5, 114.5, 124.4, 125.0,
127.5, 129.3, 130.4, 133.2, 141.2, 142.3, 162.1 ppm; LRMS: m/z calcd
for C15H13O3S (M + H): 274, found: 274.
(E)-1-Hydroxyl-4-(2-(phenylsulfonyl)vinyl)benzene (3d).
CuO (7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI
(124.5 mg, 0.75 mmol, 1.5 equiv), 4-hydroxylcinnamic acid (82 mg,
0.5 mmol, 1 equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol,
3 equiv) in DMSO (2 mL) at room temperature. The reaction was
stirred at 100 °C for 24 h under air. The reaction mixture was then
allowed to cool to room temperature, after which the crude reaction
mixture was loaded directly onto a column of silica gel and purified by
column chromatography to give the vinyl sulfone (44.2 mg, 34%).
Flash chromatography (petroleum ether/ethyl acetate, 2/1); pale
yellow oil; 1H NMR (CDCl3, 400 MHz) δ 6.66 (d, J = 16.0 Hz, 1 H),
6.86 (d, J = 8.0 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.51−7.61 (m, 4
H), 7.92 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 101 MHz) δ 116.3,
123.3, 124.3, 127.4, 129.4, 130.7, 133.5, 140.7, 143.0, 159.4 ppm;
LRMS: m/z calcd for C14H12O3S (M + H): 260, found: 260.
16.0 Hz, 1 H), 7.55−7.60 (m, 4 H), 7.64−7.70 (m, 2 H), 8.00 (d, J =
8.0 Hz, 2 H), 8.12 (d, J = 8.0 Hz, 1 H), 8.17 (d, J = 16.0 Hz, 1 H); 13
C
NMR (CDCl3, 101 MHz) δ 125.2, 128.0, 129.0, 129.5, 129.6, 131.2,
132.2, 133.8, 134.1, 139.2, 139.8, 147.9 ppm; Anal.Calcd for
C14H11NO4S Elemental Analysis: C, 58.12; H, 3.83; N, 4.84; Found:
C, 58.02; H, 3.91; N, 4.72.
(E)-1-Fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (3i). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), 4-fluorocinnamic acid (83 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (96.9 mg, 74%). Flash
chromatography (petroleum ether/ethyl acetate, 2/1); colorless solid,
1
mp = 108.5−110.6 °C; H NMR (CDCl3, 400 MHz) δ 6.80 (d, J =
16.0 Hz, 1 H), 7.09 (t, J = 8.0 Hz, 2 H), 7.47−7.68 (m, 6 H), 7.95 (d, J
= 8.0 Hz, 2 H); 13C NMR (CDCl3, 101 MHz) δ 116.3 (d, JC−F = 22.0
Hz), 127.0 (d, JC−F = 2.0 Hz), 127.7, 128.6, 129.4, 130.6 (d, JC−F = 9.0
Hz), 133.5, 140.6, 141.2, 164.6 (d, JC−F = 252.0 Hz) ppm; Anal.Calcd
for C14H11FO2S Elemental Analysis: C, 64.11; H, 4.23; Found: C,
64.01; H, 4.35.
(E)-1-Chloro-4-(2-(phenylsulfonyl)vinyl)benzene (3j). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), 4-chlorocinnamic acid (91 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (94.5 mg, 68%). Flash
chromatography (petroleum ether/ethyl acetate, 5/1); colorless solid,
(E)-1-Nitro-4-(2-(phenylsulfonyl)vinyl)benzene (3e). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), 4-nitrocinnamic acid (96.5 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (95.4 mg, 66%). Flash
chromatography (petroleum ether/ethyl acetate, 3/1); yellow solid,
1
mp = 128.5−130.8 °C; H NMR (CDCl3, 400 MHz) δ 6.86 (d, J =
16.0 Hz, 1 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.42 (d, J = 8.0 Hz, 2 H), 7.56
(t, J = 8.0 Hz, 2 H),7.62−7.66 (m, 2 H), 7.95 (d, J = 8.0 Hz, 2 H); 13C
NMR (CDCl3, 101 MHz) δ 127.7, 127.9, 129.4, 129.4, 129.8, 130.9,
133.6, 137.3, 140.5, 141.0 ppm; Anal.Calcd for C14H11ClO2S
Elemental Analysis: C, 60.32; H, 3.98; Found: C, 60.20; H, 4.08.
(E)-1-Bromo-4-(2-(phenylsulfonyl)vinyl)benzene (3k). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), 4-bromocinnamic acid (113.5 mg, 0.5
mmol, 1 equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3
equiv) in DMSO (2 mL) at room temperature. The reaction was
stirred at 100 °C for 24 h under air. The reaction mixture was then
allowed to cool to room temperature, after which the crude reaction
mixture was loaded directly onto a column of silica gel and purified by
column chromatography to give the vinyl sulfone (137.3 mg, 85%).
Flash chromatography (petroleum ether/ethyl acetate, 5/1); colorless
solid, mp = 152.3−154.5 °C; 1H NMR (CDCl3, 400 MHz) δ 6.86 (d, J
= 16.0 Hz, 1 H), 7.35 (d, J = 8.0 Hz, 2 H), 7.52−7.66 (m, 6 H), 7.95
(d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 101 MHz) δ 125.7, 127.7,
128.0, 129.4, 129.9, 131.3, 132.4, 133.6, 140.4, 141.1 ppm; Anal.Calcd
for C14H11BrO2S Elemental Analysis: C, 52.03; H, 3.43; Found: C,
51.91; H, 3.54.
1
mp = 170.2−172.3 °C; H NMR (CDCl3, 400 MHz) δ 7.04 (d, J =
16.0 Hz, 1 H), 7.59 (t, J = 8.0 Hz, 2 H), 7.67 (d, J = 8.0 Hz, 3 H), 7.74
(d, J = 12.0 Hz, 1 H), 7.97 (d, J = 8.0 Hz, 2 H), 8.25 (d, J = 8.0 Hz, 2
H); 13C NMR (CDCl3, 101 MHz) δ 124.3, 127.9, 129.3, 129.6, 131.7,
134.0, 138.4, 139.3, 139.8, 149.0 ppm; Anal.Calcd for C14H11NO4S
Elemental Analysis: C, 58.12; H, 3.83; N, 4.84; Found: C, 58.01; H,
3.95; N, 4.74.
(E)-3-Nitro-4-(2-(phenylsulfonyl)vinyl)benzene (3f). CuO (7.9
mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75
mmol, 1.5 equiv), 3-nitrocinnamic acid (96.5 mg, 0.5 mmol, 1 equiv),
and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in DMSO
(2 mL) at room temperature. The reaction was stirred at 100 °C for 24
h under air. The reaction mixture was then allowed to cool to room
temperature, after which the crude reaction mixture was loaded
directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (98.3 mg, 68%). Flash
chromatography (petroleum ether/ethyl acetate, 4/1); colorless solid,
1
mp = 136.5−138.8 °C; H NMR (CDCl3, 400 MHz) δ 7.05 (d, J =
16.0 Hz, 1 H), 7.57−7.69 (m, 4 H), 7.674 (d, J = 16.0 Hz, 1 H), 7.82
(d, J = 8.0 Hz, 1 H), 7.98 (d, J = 8.0 Hz, 2 H), 8.26 (d, J = 8.0 Hz, 1
H), 8.35 (s, 1 H); 13C NMR (CDCl3, 101 MHz) δ 122.8, 125.4, 127.9,
129.6, 130.3, 130.7, 133.9, 134.1, 134.3, 139.4, 139.9, 148.7 ppm;
Anal.Calcd for C14H11NO4S Elemental Analysis: C, 58.12; H, 3.83; N,
4.84; Found: C, 58.04; H, 3.90; N, 4.74.
(E)-1-(Pyridine-3-yl)-2-phenylsulfonylethene (3l). CuO (7.9
mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75
mmol, 1.5 equiv), 3-(3-pyridinyl)acrylic acid (74.5 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (82.1 mg, 67%). Flash
chromatography (petroleum ether/ethyl acetate, 1/1); yellow solid,
mp = 94.2−96.6 °C; 1H NMR (CDCl3, 400 MHz) δ 7.02 (d, J = 16.0
Hz, 1 H), 7.34−7.37 (m, 1 H), 7.28 (t, J = 8.0 Hz, 2 H), 7.64−7.72
(m,2 H), 7.82 (d, J = 8.0 Hz, 1 H), 7.87 (d, J = 8.0 Hz, 1 H), 8.63 (s, 1
H), 8.73 (s, 1 H); 13C NMR (CDCl3, 101 MHz) δ 123.9, 127.8, 128.3,
129.5, 129.6, 133.8, 134.9, 138.8, 140.1, 150.0, 151.8 ppm; Anal.Calcd
(E)-2-Nitro-4-(2-(phenylsulfonyl)vinyl)benzene (3g). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), 2-nitrocinnamic acid (96.5 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (104.0 mg, 72%). Flash
chromatography (petroleum ether/ethyl acetate, 3/1); yellow solid,
1
mp = 101.2−103.4 °C; H NMR (CDCl3, 400 MHz) δ 6.81 (d, J =
E
dx.doi.org/10.1021/jo5010845 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
for C13H11NO2S Elemental Analysis: C, 63.65; H, 4.52; N, 5.71;
Found: C, 63.54; H, 4.64; N, 5.60.
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (89.0 mg, 64%). Flash
chromatography (petroleum ether/ethyl acetate, 10/1); colorless solid,
mp = 86.2−88.2 °C; 1H NMR (CDCl3, 400 MHz) δ 6.86 (d, J = 16.0
Hz, 1 H), 7.39−7.44 (m, 3 H), 7.50 (t, J = 8.0 Hz, 4 H), 7.69 (d, J =
16.0 Hz, 1 H), 7.89 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 101
MHz) δ 126.8, 128.7, 129.1, 129.2, 129.7, 131.5, 132.2, 139.3, 140.1,
143.1 ppm; Anal.Calcd for C14H11ClO2S Elemental Analysis: C, 60.32;
H, 3.98; Found: C, 60.22; H, 4.10.
(E)-1-(Pyridine-2-yl)-2-phenylsulfonylethene (3m). CuO (7.9
mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75
mmol, 1.5 equiv), 3-(2-pyridinyl)acrylic acid (74.5 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (76.0 mg, 62%). Flash
chromatography (petroleum ether/ethyl acetate, 5/1); yellow solid,
mp = 85.2−87.4 °C; 1H NMR (CDCl3, 400 MHz) δ 7.29−7.32 (m, 1
H), 7.41−7.48 (m, 2 H), 7.55 (t, J = 8.0 Hz, 2 H), 7.61−7.68 (m, 2
H), 7.75 (t, J = 8.0 Hz, 1 H), 7.97 (d, J = 8.0 Hz, 2 H), 8.62 (d, J = 6.8
Hz, 1 H); 13C NMR (CDCl3, 101 MHz) δ 125.1, 125.5, 127.9, 129.4,
131.8, 133.6, 137.1, 140.2, 140.6, 150.3, 151.0 ppm; Anal.Calcd for
C13H11NO2S Elemental Analysis: C, 63.65; H, 4.52; N, 5.71; Found:
C, 63.53; H, 4.62; N, 5.61.
(E)-1-Methylsulfonyl-2-phenylethene (3r). CuO (7.9 mg, 0.1
mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75 mmol,
1.5 equiv), cinnamic acid (74 mg, 0.5 mmol, 1 equiv), and sodium
methylsulfinate (306 mg, 3.0 mmol, 3 equiv) in DMSO (2 mL) at
room temperature. The reaction was stirred at 100 °C for 24 h under
air. The reaction mixture was then allowed to cool to room
temperature, after which the crude reaction mixture was loaded
directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (30.0 mg, 33%). Flash
chromatography (petroleum ether/ethyl acetate, 2/1); colorless oil;
1H NMR (CDCl3, 400 MHz) δ 3.04 (s, 1 H), 6.92 (d, J = 16.0 Hz, 1
H), 7.42−7.53 (m, 5 H), 7.64 (d, J = 16.0 Hz, 1 H); 13C NMR
(CDCl3, 101 MHz) δ 43.3, 126.1, 128.6, 129.2, 131.5, 132.1, 144.1
ppm; LRMS: m/z calcd for C9H10O2S (M + H): 182, found: 182.
(E)-1-Hydroxyl-2-(2-(phenylsulfonyl)vinyl)benzene (3s). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg,
0.75 mmol, 1.5 equiv), 2-hydroxylcinnamic acid (82 mg, 0.5 mmol, 1
equiv), and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (41.6 mg, 32%). Flash
chromatography (petroleum ether/ethyl acetate, 3/1); colorless solid,
mp = 159.2−161.8 °C; 1H NMR (DMSO-d6, 400 MHz) δ 10.53 (brs,
1 H), 7.91−7.93 (m, 2 H), 7.84 (d, J = 16.0 Hz, 1 H), 7.61−7.70 (m, 4
H), 7.46 (d, J = 16.0 Hz, 1 H), 7.27 (t, J = 8.0 Hz, 1 H), 6.94 (d, J =
8.0 Hz, 1 H), 6.83 (t, J = 8.0 Hz, 1 H); 13C NMR (DMSO-d6, 101
MHz) δ 116.6, 119.2, 119.8, 127.1, 127.4, 129.9, 130.2, 133.0, 133.7,
137.9, 141.4, 157.5 ppm; Anal. Calcd for C14H12O3S Elemental
Analysis: C, 64.60; H, 4.65; Found: C, 64.65; H, 4.58.
(E)-1-(Furan-2-yl)-2-phenylsulfonylethene (3n). CuO (7.9 mg,
0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75
mmol, 1.5 equiv), 3-(2-furyl)acrylic acid (69 mg, 0.5 mmol, 1 equiv),
and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in DMSO
(2 mL) at room temperature. The reaction was stirred at 100 °C for 24
h under air. The reaction mixture was then allowed to cool to room
temperature, after which the crude reaction mixture was loaded
directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (66.7 mg, 57%). Flash
chromatography (petroleum ether/ethyl acetate, 5/1); colorless oil;
1H NMR (CDCl3, 400 MHz) δ 6.49 (d, J = 6.2 Hz, 1 H), 6.71−6.75
(m, 2 H), 7.43−7.48 (m, 2 H), 7.54 (t, J = 8.0 Hz, 2 H), 7.61 (t, J =
8.0 Hz, 1 H), 7.93 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 101 MHz)
δ 112.6, 117.0, 124.7, 127.6, 128.9, 129.3, 133.3, 140.9, 145.7, 148.7
ppm; LRMS: m/z calcd for C12H10O3S (M + H): 234, found: 234.
(E)-1-(Thiophen-2-yl)-2-phenylsulfonylethene (3o). CuO (7.9
mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5 mg, 0.75
mmol, 1.5 equiv), 3-(2-thienyl)acrylic acid (77 mg, 0.5 mmol, 1 equiv),
and sodium benzenesulfinate (246 mg, 1.5 mmol, 3 equiv) in DMSO
(2 mL) at room temperature. The reaction was stirred at 100 °C for 24
h under air. The reaction mixture was then allowed to cool to room
temperature, after which the crude reaction mixture was loaded
directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (75.0 mg, 60%). Flash
1
chromatography (petroleum ether/ethyl acetate, 5/1); yellow oil; H
ASSOCIATED CONTENT
NMR (CDCl3, 400 MHz) δ 6.57 (d, J = 16.0 Hz, 1 H), 6.99 (d, J = 6.2
Hz, 1 H), 7.23 (s, 1 H), 7.35 (d, J = 8.0 Hz, 1 H), 7.44−7.58 (m, 3 H),
7.71 (d, J = 16.0 Hz, 1 H), 7.85 (d, J = 8.0 Hz, 2 H); 13C NMR
(CDCl3, 101 MHz) δ 125.4, 127.6, 128.4, 129.4, 130.1, 132.6, 133.4,
135.2, 136.9, 140.8 ppm; LRMS: m/z calcd for C12H10O2S2 (M + H):
250, found: 250.
■
S
* Supporting Information
1
Copies of H and 13C NMR spectra for the products. This
material is available free of charge via the Internet at http://
pubs.acs.org.
(E)-1-(4-Methylphenyl)sulfonyl-2-phenylethene (3p). CuO
(7.9 mg, 0.1 mmol, 0.2 equiv) was added to a mixture of KI (124.5
mg, 0.75 mmol, 1.5 equiv), cinnamic acid (74 mg, 0.5 mmol, 1 equiv),
and sodium 4-methylbenzenesulfinate (267 mg, 1.5 mmol, 3 equiv) in
DMSO (2 mL) at room temperature. The reaction was stirred at 100
°C for 24 h under air. The reaction mixture was then allowed to cool
to room temperature, after which the crude reaction mixture was
loaded directly onto a column of silica gel and purified by column
chromatography to give the vinyl sulfone (72.2 mg, 56%). Flash
chromatography (petroleum ether/ethyl acetate, 8/1); colorless solid,
mp = 112.3−114.6 °C; 1H NMR (CDCl3, 400 MHz) δ 2.43 (s, 1 H),
6.85 (d, J = 16.0 Hz, 1 H), 7.30−7.48 (m, 7 H), 7.66 (d, J = 16.0 Hz, 1
H), 7.83 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 101 MHz) δ 21.7,
127.6, 127.7, 128.6, 129.1, 130.0, 131.1, 132.5, 137.7, 142.0, 144.4
ppm; Anal.Calcd for C15H14O2S Elemental Analysis: C, 69.74; H, 5.46;
Found: C, 69.68; H, 5.58.
AUTHOR INFORMATION
Corresponding Author
*E-mail: ccguo@hnu.edu.cn.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for the financial support from the National
Natural Science Foundation of China (21372068, J1210040,
J1103312) and the Presidential Scholarship for Doctoral
Students, Hunan University.
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