Metal-free synthesis of (E)-vinyl sulfones via denitrative coupling reactions of β-nitrostyrenes with sodium sulfinates

Article abstract of DOI:10.1080/10426507.2018.1513518

A practical metal-free procedure for the synthesis of (E)-vinyl sulfones has been developed through the coupling of β-nitrostyrenes with sodium sulfinates under microwave irradiation. This methodology provides a convenient and efficient approach to various (E)-vinyl sulfones from readily available starting materials with excellent regioselectivity. The present oxidative reaction involves an efficient denitrative radical cross-coupling of β-nitrostyrenes with sodium sulfinates via using AcOH as an additive.

Full text of DOI:10.1080/10426507.2018.1513518

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Metal-free synthesis of (E)-vinyl sulfones via
denitrative coupling reactions of β-nitrostyrenes
with sodium sulfinates
Guang-Feng Hong, Jin-Wei Yuan, Zhen-Hua Dong, Yong-Mei Xiao, Pu Mao &
Ling-Bo Qu
To cite this article: Guang-Feng Hong, Jin-Wei Yuan, Zhen-Hua Dong, Yong-Mei Xiao, Pu Mao &
Ling-Bo Qu (2018): Metal-free synthesis of (E)-vinyl sulfones via denitrative coupling reactions of
β-nitrostyrenes with sodium sulfinates, Phosphorus, Sulfur, and Silicon and the Related Elements,
DOI: 10.1080/10426507.2018.1513518
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1513518
Metal-free synthesis of (E)-vinyl sulfones via denitrative coupling reactions of
b-nitrostyrenes with sodium sulfinates
Guang-Feng Honga, Jin-Wei Yuanb, Zhen-Hua Dongb, Yong-Mei Xiaob, Pu Maob, and Ling-Bo Qub,c
b
aZhengzhou Tobacco Research Institute of CNTC, Zhengzhou, PR China; School of Chemistry & Chemical Engineering, Henan University of
c
Technology; Academician Workstation for Natural Medicinal Chemistry of Henan Province, Zhengzhou, PR China; College of Chemistry and
Molecular Engineering, Zhengzhou University, Zhengzhou, PR China
ABSTRACT
ARTICLE HISTORY
Received 17 April 2018
Accepted 9 August 2018
A practical metal-free procedure for the synthesis of (E)-vinyl sulfones has been developed
through the coupling of b-nitrostyrenes with sodium sulfinates under microwave irradiation. This
methodology provides a convenient and efficient approach to various (E)-vinyl sulfones from read-
ily available starting materials with excellent regioselectivity. The present oxidative reaction
involves an efficient denitrative radical cross-coupling of b-nitrostyrenes with sodium sulfinates via
using AcOH as an additive.
KEYWORDS
b-nitrostyrene; sodium
sulfinate; acid-promotion;
radical reaction;
sulfonylation
GRAPHICAL ABSTRACT
Introduction
stoichiometric oxidants,[24, 30] the coupling reactions of alkenes
or cinnamic acids with sulfonyl halides, and sulfonyl hydra-
zides;[31–38] and the addition of sulfinic acids, sulfonyl hydra-
zides, or dimethyl sulfoxide to alkynes.[39–43] Nevertheless,
most of these reactions might suffer from some limitations,
such as the need of inaccessible starting materials, tedious pro-
cedures, harsh reaction conditions, low atom economy, and
poor regioselectivity or toxic metal catalysis.
Sodium arenesulfinates are readily accessible synthetic
intermediates that can be used as aryl sources by means of
C-S bond cleavage. More significantly, they could also serve
as sulfone or thioether sources.[44–47] Compared to other
sulfenylation/sulfonation agents, sodium arenesulfinates are
relative stable and moisture-insensitive.[48–51] They have
been widely used as arylsulfonylation reagents for preparing
organosulfonyl compounds.[52–55] Recently, the oxidative
cross-coupling reaction of alkenes or cinnamic acids with
sodium sulfinates has been developed (Scheme 1a).[56–67]
Nitro-olefins are relatively stable, simply obtained by Henry
reaction from aldehydes and nitromethane, which have been
widely used to synthesized useful organic molecules. In
Vinyl sulfones as an important class of sulfur-containing com-
pounds play a significant role in organic synthesis and material
sciences due to the chemical versatility of the sulfonyl moi-
ety.[1–10] Vinyl sulfone containing molecules have been shown
to exhibit important biological activities; for example, as cyst-
eine protease inhibitors,[11–14] HIV-1 inhibitors,[15] and inhibi-
tors of sortase, and protein tyrosine phosphatases.[16–19] Owing
to the significance of these compounds, various approaches to
produce vinyl sulfones have been developed. Traditionally,
Knoevenagel condensation of aromatic aldehydes with sulfo-
nylacetic acids,[20] b-elimination of selenosulfones or halosul-
fones,[21,22] Wittig reaction of a-sulfinylphosphonium ylides,[23]
and the oxidation of the corresponding sulfides[24,25] are per-
haps the most common methods. However, these methods suf-
fer from inaccessible substrates, the multi-steps, strong bases
and strong oxidants involved in these transformations, which
limits their wide application. Recently, a series of alternative
methods for vinyl sulfones synthesis have also been developed,
such as the transition-metal-catalyzed cross-coupling of sulfi-
nate salts with vinyl bromides, vinyl triflates, or vinylboronic
acids;[26–29] the oxidation of preformed vinyl sulfides with some cases, b-nitrostyrenes have been used for denitrative
CONTACT Jin-Wei Yuan
yuanjinweigs@126.com
School of Chemistry & Chemical Engineering, Henan University of Technology; Academician Workstation
for Natural Medicinal Chemistry of Henan Province, Zhengzhou 450001, PR China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
Supplemental data for this article can be accessed at https://doi.org/10.1080/10426507.2018.1513518.
ß 2018 Taylor & Francis Group, LLC

2
G.-F. HONG ET AL.
Previous works:
This work:
Scheme 1. Synthesis of (E)-vinyl sulfones from sodium sulfinates and alkene derivatives.
C-C bond formation by an addition/elimination reac- respectively. They have a coupling constant JH-H ¼ 15.4 Hz
tion.[68–71] In 2016, Yadav’s group reported a silver-catalyzed typical of trans positioned protons, which proves that con-
coupling reaction of nitro-olefins and sodium sulfinates in figuration of 3aa is an E stereoisomer. Encouraged by this
the presence of oxidant and under nitrogen atmosphere.[72]
result, we examined some different protic acids. However,
Subsequently,
a Mn(III)-mediated coupling reaction of
moderate yields were achieved when several inorganic and
organic acids such as H2SO4, HNO3, TsOH, TFA, and
MeSO3H were used (Table 1, entries 3–6, 8, 9). It was pleas-
ing to find that 70% of 3aa was isolated when AcOH was
employed in the reaction (Table 1, entry 7). The suitable
amount of AcOH was subsequently screened (Table 1,
entries 7, 10–12). The results indicated that increasing or
decreasing the amount of AcOH did not increase the yield.
Then, the screening of a range of solvents demonstrated that
the reaction performed in DMSO was significantly better
than those conducted in H2O, CH3CN, 1,4-dioxane,
CH3OH, DCE, and THF (Table 1, entries 7, 13–18). The
ratio of (E)-b-nitrostyrene with sodium 4-methylbenzenesul-
finate was investigated, and the ratio of 1:1.5 proved to give
the best result, providing 70% yield of 3aa (Supporting
information, Table S1, entries 1–4). Next, various reaction
temperatures were also examined, and 90 ꢀC was found to
be the best choice (Table 1, entries 7, 19–21). Finally, the
effect of reaction time was investigated, and good yields
(80%) could be obtained in 40 min (Table 1, entries 7,
22–25). Therefore, the optimal reaction conditions are: 1.5
equiv of sodium sulfinate, and 2.0 equiv of AcOH in DMSO
at 90 ꢀC for 40 min under microwave irradiation as shown
in Table 1, entry 24.
Under the optimized conditions in hand, the scope of the
AcOH-mediated oxidative coupling of b-nitrostyrenes with
various sodium arenesulfinates for the construction of (E)-
vinyl sulfones was explored. The results are summarized in
Table 2. In general, the reaction worked very well for a
range of sodium arenesulfinates with various substituents at
the phenyl ring, and the products were isolated in yields
ranging from 38% to 85%. Sodium arenesulfinates with elec-
tron-donating substituents at the phenyl ring afforded the
desired vinyl sulfones in 78% to 85% yield (3aa–3ad),
whereas sodium arenesulfinates bearing electron-withdraw-
sodium sulfinates with nitro-olefins has also been developed
by Chen’s group (Scheme 1b).[73] Despite some great advan-
tage of these reactions, there are still certain limitations
including harsh reaction conditions and toxic metal catalysts.
Therefore, it still remains an attractive task to develop more
economic, efficient, and highly selective methods to access
vinyl sulfones under metal-free conditions. The present proto-
col of AcOH-mediated direct oxidative coupling b-nitrostyr-
enes with sodium sulfinates under microwave irradiation
provides a facile and efficient approach to various (E)-vinyl
sulfones in moderate to good yields (Scheme 1c). The advan-
tages of this approach are commercially available substrates,
high regioselectivity, and avoidance to use any metal catalyst.
Results and discussion
Initially, (E)-b-nitrostyrene (1a) and sodium 4-methylbenze-
nesulfinate (2a) were selected as the model substrates to
optimize the reaction conditions under microwave irradi-
ation. As shown in Table 1, only a trace amount of desired
product 3aa was obtained when the model reaction was per-
formed at 80 ꢀC in DMSO for 20 min under microwave
irradiation (Table 1, entry 1). Vinyl sulfones have been effi-
ciently synthesized by treatment of alkenes with sodium are-
nesulfinates using potassium iodide and sodium periodate in
the presence of a catalytic amounts of acetic acid by Das’
group,[74] and Zhang’s group has also developed a phos-
phoric acid-mediated synthesis of vinyl sulfones through
decarboxylative coupling reactions of sodium sulfinates with
phenylpropiolic acids.[34] These facts showed that the acid
plays an important role for this cross-coupling reactions.
We envisioned whether the acid could promote this trans-
formation. When 2.0 equiv H3PO4 was added to the reaction
system, much to our excitement 40% of 3aa was obtained
(Table 1, entry 2). The E or Z stereochemistry of 3aa is eas- ing substituents at the phenyl ring provided the desired
1
ily established by the H NMR analysis. The chemical shifts vinyl sulfones in 38%–55% yield (3ae–3ai). Especially, the
of the a- and b-protons are 7.65 ppm and 6.85 ppm, strong electron-withdrawing trifluoromethyl group (CF3) at

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Table 1. Optimization of reaction conditions.a
Entry
Additive (eq.)
Solvent
DMSO
Temp (oC)
Time (mins)
Yieldb (%)
1
–
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
70
90
100
90
90
90
90
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
10
30
40
60
trace
40
48
<5
40
45
70
35
53
10
48
50
trace
50
45
65
50
60
65
75
73
30
77
80
80
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
H3PO4 (2.0)
H2SO4 (2.0)
HCl (2.0)
HNO3 (2.0)
TsOH (2.0)
AcOH (2.0)
TFA (2.0)
MeSO3H (2.0)
AcOH (0.5)
AcOH (1.0)
AcOH (3.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
AcOH (2.0)
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
H2O
CH3CN
1,4-dioxane
CH3OH
DCE
THF
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
aReaction conditions: (E)-(2-nitrovinyl)benzene 1a (0.2 mmol, 29.8 mg), sodium 4-methylbenzenesulfi-
nate 2a (0.3 mmol, 53.4 mg), additive and solvent (2.0 mL) under microwave irradiation.
bIsolated yield.
the para-position of the phenyl ring had a noticeable effect, 35% yield when 1.5 equiv. 2,2,6,6-tetramethylpiperidinyloxy
resulting in relatively lower yield (3ah). It was found that (TEMPO), a radical scavenger, was added into the reaction
halogen substituents, such as F, Cl, and Br, were all well tol- system. Only trace amounts of product (3aa) were dectected
erated, which made this protocol more useful for further in the presence of TEMPO (2.5 equiv). These facts indicated
that the reaction might occur via a radical mechanism.
Based on the above experimental results and previous
reports,[34,73–75] a possible reaction pathway was proposed as
shown in Scheme 3. Initially, the benzenesulfinate anion is
oxidized by DMSO via a single electron transfer (SET)
to induce the formation of a radical (i. e. a resonance hybrid
A $ B).[76,77] Subsequently, this radical selectively adds to
the b-position of (E)-b-nitrostyrene to form a carbon-cen-
tered radical C. The benzyl radical C adopts a more stable
conformation D, and subsequently abstracts a hydrogen rad-
ical from AcOH to form the compound E. AcOH could also
act as a protonating reagent during the reaction.[34] Finally,
E is converted to the desired product 3ab by elimination
of HNO2.
structural modification (3ae–3ag, 3ai). To our delight, sodium
2-chlorobenzenesulfinate 2i reacted smoothly with b-nitro-
styrene, resulting in a moderate yield of the desired product
3ai (55%), which showed that the steric effect played a weak
role during this transformation. It is noteworthy that sodium
alkanesulfinates, such as sodium methanesulfinate, sodium
ethanesulfinate, and sodium cyclopropanesulfinate, could also
be used in the reactions to give the corresponding products
3aj, 3ak, and 3al in moderate yields. The scope of this oxida-
tive coupling reaction was further expanded to a variety of
substituted b-nitrostyrenes. Substituted b-nitrostyrenes with
electron-donating substituents and with electron-withdrawing
substituents were all tolerated under the standard reaction
conditions (3bb–3bd). Unfortunately, when other substrates
such as styrenes and cinnamic acid were employed for this
coupling reaction, the desired products were not formed
under the present conditions.
Conclusion
In order to gain some further insight into the reaction
mechanism, several control experiments were carried out
(Scheme 2). Initially, (E)-1-methyl-4-(styrylsulfonyl)benzene
In summary, we have developed an efficient and practical
method for the preparation of (E)-vinyl sulfones via AcOH-
promoted oxidative cross-coupling reaction of b-nitrostyr-
(3aa) was isolated in 80% yield when the reaction of enes with sodium sulfinates. This reaction is initiated by
b-nitrostyrene with sodium 4-methylbenzenesulfinate was generation of a sulfonyl radical from the sodium sulfinate. A
conducted under the standard conditions. However, (E)-1- plausible reaction mechanism is proposed on the basis of
methyl-4-(styrylsulfonyl)benzene (3aa) was isolated in only control experiments.

4
G.-F. HONG ET AL.
Table 2. Synthesis of (E)-vinyl sulfones from b-nitrostyrenes with sodium
br ¼ broad), coupling constant in Hz and integration.
Chemical shifts for 13C NMR spectra were recorded in ppm
from tetramethylsilane. MS were obtained on a Thermo
Scientific LTQ Orbitrap XL instrument using the ESI tech-
nique. IR spectra, ꢀ(cmꢁ1), were recorded on a Shimadazu
IR-408 FTIR spectrophotometer using a thin film supported
on KBr pellets. Melting points were measured on an XT4A
microscopic apparatus uncorrected. The Supplemental
Materials contains additional catalyst and product character-
ization results (Figures S 1–S 4).
sulfinates.a,b
General experimental procedure for the synthesis of (E)-
vinyl sulfones (3)
b-Nitrostyrenes 1 (0.2 mmol), sodium sulfinate 2 (0.3 mmol),
and AcOH (0.4 mmol, 24 mg) in DMSO (2 mL) were added
to a 5.0 mL microwave reaction tube. The reactant mixture
was heated at 90 ꢀC for 40 min under microwave irradiation.
After completion of the reaction, the solvent was distilled
under vacuum. The residue was dissolved in EtOAc (10 mL),
washed with 10% NaHCO3 (10 mL ꢂ2), then washed with
saturated brine (10 mL ꢂ2). The organic phase was dried
over anhydrous Na2SO4 and concentrated under vacuum.
The crude product was purified by silica gel column chro-
matography to give the desired products 3.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3aa)
Light yellow solid, mp 95–96 ꢀC [lit.[26] mp 98–99 ꢀC]. IR:
1
2956, 2918, 2850, 1617, 1558, 1250, 1144. H NMR d: 7.82
(d, JH-H ¼ 8.2 Hz, 2H), 7.65 (d, JH-H ¼ 15.4 Hz, 1H), 7.48-
7.46 (m, 2H), 7.39-7.33 (m, 5H), 6.85 (d, JH-H ¼ 15.4 Hz,
1H), 2.43 (s, 3H). 13C NMR d: 144.4, 141.9 (CH), 137.7,
132.5, 131.1 (CH), 129.9 (CH), 129.0 (CH), 128.5 (CH),
127.7 (CH), 127.6 (CH), 21.6 (CH3). MS m/z: 259.2
[M þ H]þ (calcd for C15H15O2Sþ 259.1).
(E)-[2-(Benzenesulfonyl)vinyl]benzene (3ab)
aReaction conditions: b-nitrostyrenes
1 (0.2 mmol), sodium sulfinate 2
Colorless solid, mp 74–75 ꢀC [lit.[78] mp 75–76 ꢀC]. IR: 2956,
(0.3 mmol), and AcOH (0.4 mmol, 24 mg) in 2.0 mL DMSO solvent, 90 ꢀC for
40 min under microwave irradiation.
1
2920, 2850, 1558, 1446, 1308, 1147, 1086. H NMR d: 7.95
bIsolated yield.
(d, JH-H ¼ 7.2 Hz, 2H), 7.69 (d, JH-H ¼ 15.4 Hz, 1H), 7.64-
7.60 (m, 1H), 7.55 (t, JH-H ¼ 7.8 Hz, 2H), 7.50-7.47 (m, 2H),
7.42-7.39 (m, 3H), 6.86 (d, JH-H ¼ 15.4 Hz, 1H). 13C NMR d:
142.5 (CH), 140.7, 133.4 (CH), 132.3, 131.2 (CH), 129.4
(CH), 129.1 (CH), 128.6 (CH), 127.7 (CH), 127.3 (CH). MS
m/z: 244.3 [M þ H]þ (calcd for C14H12O2Sþ 244.1).
Experimental
General information
All substrates purchased from J & K Scientific Ltd. were
used without further purification. Column chromatography
was performed using 300–400 mesh silica with the indicated
solvent system according to standard techniques. A CEM
Discover microwave reactor with an infrared pyrometer and
a pressure control system was used. NMR spectra were
recorded in CDCl3 on a Bruker Avance 400 spectrometer
(E)-1-tert-Butyl-4-(styrylsulfonyl)benzene (3ac)[33]
Light yellow solid, mp 98–100 ꢀC. IR: 2956, 2927, 2856,
1
1743, 1558, 1309, 1147. H NMR d: 7.86 (d, JH-H ¼ 8.5 Hz,
2H), 7.66 (d, JH-H ¼ 15.4 Hz, 1H), 7.55 (d, JH-H ¼ 8.5 Hz,
2H), 7.48-7.46 (m, 2H), 7.39-7.35 (m, 3H), 6.68 (d, JH-
(1H: 400 MHz, 13C: 100 MHz). Chemical shifts for H NMR
spectra are recorded in ppm from tetramethylsilane. Data
were reported as follows: chemical shift, multiplicity
1
¼ 15.4 Hz, 1H), 1.33 (s, 9H). 13C NMR d: 157.4, 141.9
H
(CH), 137.7, 132.5, 131.1 (CH), 129.1 (CH), 128.5 (CH),
127.7 (CH), 127.6 (CH), 126.4 (CH), 35.3, 31.0 (CH3). MS
(s ¼ singlet, d ¼ doublet, t ¼ triplet, m ¼ multiplet and m/z: 301.0 [M þ H]þ (calcd for C18H21O2Sþ 301.1).

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Scheme 2. Control experiments.
Scheme 3. Proposed reaction mechanism.
(E)-1-Methoxy-4-(styrylsulfonyl)benzene (3ad)
(E)-1-Bromo-4-(styrylsulfonyl)benzene (3ag)
Light yellow solid, mp 110–111 ꢀC [lit.[72] mp 109–111 ꢀC]. Light yellow solid, mp 110–112 ꢀC [lit.[72] mp 113–117 ꢀC]. IR:
1
1
IR: 2956, 2918, 2850, 1596, 1558, 1506, 261, 1142, 1086. H
2956, 2918, 2850, 1558, 1315, 1142, 1082. H NMR d: 7.80 (d,
NMR d: 7.87 (d, JH-H ¼ 8.9 Hz, 2H), 7.64 (d, JH-H ¼ 15.4 Hz,
JH-H ¼ 8.4 Hz, 2H), 7.71-7.67 (m, 3H), 7.48 (d, JH-H ¼ 7.4 Hz,
2H), 7.43-7.38 (m, 3H), 6.83 (d, JH-H ¼ 15.4 Hz, 1H). 13C
NMR d: 143.1 (CH), 139.8, 132.7 (CH), 132.2, 131.4 (CH),
129.2 (CH), 129.1 (CH), 128.6 (CH), 126.8 (CH). MS m/z:
322.1 [M þ H]þ (calcd for C14H11BrO2Sþ 321.9).
1H), 7.48-7.46 (m, 2H), 7.39-7.38 (m, 3H), 7.01 (d, JH-H
¼
8.9 Hz, 2H), 6.85 (d, JH-H ¼ 15.4 Hz, 1H), 3.87 (s, 3H). 13C
NMR d: 163.6, 141.4 (CH), 132.5, 132.2, 131.1 (CH), 129.9
(CH), 129.1 (CH), 128.5 (CH), 127.9 (CH), 114.6 (CH), 55.7
(CH3).
MS
m/z:
275.2
[M þ H]þ
(calcd
for
C15H15O3Sþ 275.1).
(E)-1-(Styrylsulfonyl)-4-(trifluoromethyl)benzene (3ah)
(E)-1-Fluoro-4-(styrylsulfonyl)benzene (3ae)
Light yellow solid, mp 93–94 ꢀC [lit.[72] mp 79–82 ꢀC]. IR:
3047, 2960, 1734, 1558, 1321, 1144, 1061. H NMR d: 8.08
1
Colorless solid, mp 85–86 ꢀC [lit.[79] mp 85–87 ꢀC]. IR: 2956,
2924, 2850, 1591, 1558, 1495, 1319, 1290, 1144, 1086. 1H
NMR d: 7.98-7.94 (m, 2H), 7.68 (d, JH-H ¼ 15.4 Hz, 1H),
7.50-7.47 (m, 2H), 7.43-7.39 (m, 3H), 7.21 (d, JH-H ¼ 8.6 Hz,
2H), 6.84 (d, JH-H ¼ 15.4 Hz, 1H). 13C NMR d: 142.7 (CH),
132.2, 131.4 (CH), 130.5 (d, JF-C ¼ 9.5 Hz, CH), 129.2 (CH),
128.6 (CH), 127.1 (CH), 116.6 (d, JF-C ¼ 22.6 Hz, CH). 19F
NMR (376 MHz) d: ꢁ103.9. MS m/z: 262.2 [M þ H]þ (calcd
for C14H11FO2Sþ 262.0).
(d, JH-H ¼ 8.2 Hz, 2H), 7.82 (d, JH-H ¼ 8.3 Hz, 2H), 7.70 (d,
JH-H ¼ 15.4 Hz, 1H), 7.51-7.48 (m, 2H), 7.44-7.39 (m, 3H),
6.85 (d, JH-H ¼ 15.4 Hz, 1H). 13C NMR d: 144.4, 144.0 (CH),
135.0 (d, JF-C ¼ 32.9 Hz), 132.0, 131.6 (CH), 129.2 (CH),
128.7 (CH), 128.3 (CH), 126.4 (t, JF-C ¼ 3.7 Hz, CH), 126.2
(CH), 124.5. 19F NMR (376 MHz) d: -63.2. MS m/z: 312.1
[M þ H]þ (calcd for C15H11F3O2Sþ 312.0).
(E)-1-Chloro-2-(styrylsulfonyl)benzene (3ai)
(E)-1-Chloro-4-(styrylsulfonyl)benzene (3af)
Pale Yellow solid, mp 200–201 ꢀC [lit.[65] mp 75–76 ꢀC]. IR:
Colorless solid, mp 82–83 ꢀC [lit.[72] mp 78–80 ꢀC]. IR: 3128,
3039, 1610, 1576, 1473, 1394, 1315, 1147, 1086. H NMR d:
1
1
1574, 1448, 1311, 1146, 1043. H NMR d: 8.22 (dd, JH-H
¼
7.9 Hz, JH-H ¼ 1.4 Hz, 1H), 7.77 (d, JH-H ¼ 15.4 Hz, 1H),
7.56-7.38 (m, 8H), 7.08 (d, JH-H ¼ 15.4 Hz, 1H). 13C NMR d:
145.3 (CH), 138.3, 134.5 (CH), 132.8, 132.3, 131.9 (CH),
131.4 (CH), 130.7 (CH), 129.1 (CH), 128.7 (CH), 127.4
(CH), 125.4 (CH). MS m/z: 278.1 [M þ H]þ (calcd for
C14H11ClO2Sþ 278.0).
7.88 (d, JH-H ¼ 8.6 Hz, 2H), 7.68 (d, JH-H ¼ 15.4 Hz, 1H),
7.48-7.45 (m, 4H), 7.38-7.33 (m, 3H), 6.92 (d, JH-H
¼
15.4 Hz, 1H). 13C NMR d: 143.1 (CH), 139.9, 139.3, 132.2,
131.4 (CH), 129.7 (CH), 129.2 (CH), 129.1 (CH), 128.7
(CH), 126.9 (CH). MS m/z: 279.1 [M þ H]þ (calcd for
C14H12ClO2Sþ 279.0).

6
G.-F. HONG ET AL.
(E)-[2-(Methanesulfonyl)vinyl]benzene (3aj)
(E)-5-[2-(Benzenesulfonyl)vinyl]benzo[d] [1, 3]dioxole
(3db)
Colorless solid, mp 78–79 ꢀC [lit.[79] mp 79–81 ꢀC]. IR: 3045,
Colorless solid, mp 97–98 ꢀC [lit.[33] mp 95–96 ꢀC]. IR: 3058,
1
2925, 1622, 1300, 1134. H NMR d: 7.62 (d, JH-H ¼ 15.5 Hz,
1
2937, 1605, 1460, 1282, 1078. H NMR d: 7.93 (d, JH-H
¼
1H), 7.52-7.50 (m, 2H), 7.44-7.40 (m, 3H), 6.95 (d, JH-H
¼
15.5 Hz, 1H), 3.04 (s, 3H). 13C NMR d: 143.9 (CH), 132.1,
131.4 (CH), 129.2 (CH), 128.6 (CH), 126.3 (CH), 43.2 (CH3).
MS m/z: 183.1 [M þ H]þ (calcd for C9H11O2Sþ 183.0).
7.3 Hz, 2H), 7.62-7.51 (m, 4H), 6.99 (dd, JH-H ¼ 8.0 Hz,
JH-H ¼ 1.6 Hz, 1H), 6.93 (d, JH-H ¼ 1.5 Hz, 1H), 6.80 (d,
JH-H ¼ 8.0 Hz, 1H), 6.68 (d, JH-H ¼ 15.3 Hz, 1H), 5.99 (s,
2H). 13C NMR d: 150.4, 148.5, 142.3 (CH), 140.9, 133.3
(CH), 129.3 (CH), 127.5 (CH), 126.6, 125.4 (CH), 124.9
(CH), 108.7 (CH), 106.8 (CH), 101.8 (CH2). MS m/z: 289.3
[M þ H]þ (calcd for C15H13O4Sþ 289.1).
(E)-[2-(Ethanesulfonyl)vinyl]benzene (3ak)[72]
1
Pale yellow oil. IR: 3056, 2960, 1624, 1304, 1128. H NMR
d: 7.61 (d, JH-H ¼ 15.5 Hz, 1H), 7.52 (d, JH-H ¼ 7.3 Hz, 2H),
(E)-1-Fluoro-4-[2-(benzenesulfonyl)vinyl]benzene (3eb)
7.45-7.42 (m, 3H), 6.82 (d, JH-H ¼ 15.5 Hz, 1H), 3.09 (q, JH-H
¼
Colorless solid, mp 91–92 ꢀC [lit.[33] mp 92–93 ꢀC]. IR: 3057,
7.4 Hz, 2H), 1.39 (t, JH-H ¼ 7.4 Hz, 3H). 13C NMR d: 145.2
(CH), 132.3, 131.4 (CH), 129.2 (CH), 128.6 (CH), 124.0 (CH),
49.5 (CH2), 7.3 (CH3). MS m/z: 197.2 [M þ H]þ (calcd for
C10H13O2Sþ 197.1).
1
2924, 1716, 1558, 1508, 1306, 1232, 1146, 1084. H NMR d:
7.95-7.93 (m, 2H), 7.67-7.61 (m, 2H), 7.55 (t, JH-H ¼ 7.8 Hz,
2H), 7.50-7.46 (m, 2H), 7.08 (d, JH-H ¼ 8.6 Hz, 2H), 6.80 (d,
JH-H ¼ 15.4 Hz, 1H). 13C NMR d: 164.3 (d, JF-C ¼ 251.6 Hz),
141.2 (CH), 140.6, 133.5 (CH), 130.6 (d, JF-C ¼ 8.7 Hz, CH),
129.4 (CH), 128.6 (d, JF-C ¼ 3.5 Hz), 127.7 (CH), 127.0 (d,
JF-C ¼ 2.5 Hz, CH), 116.3 (d, JF-C ¼ 21.9 Hz, CH). 19F NMR
(376 MHz) d: -107.7. MS m/z: 263.3 [M þ H]þ (calcd for
C14H12FO2Sþ 263.1).
(E)-[2-(Cyclopropanesulfonyl)vinyl]benzene (3al)
Colorless solid, mp 89–90 ꢀC [lit.[80] pale yellow oil]. IR:
1
3045, 1616, 1577, 1452, 1317, 1292, 1126, 1038. H NMR d:
7.56-7.50 (m, 3H), 7.45-7.38 (m, 3H), 6.93 (d, JH-H
¼
15.5 Hz, 1H), 2.49-2.43 (m, 1H), 1.30-1.26 (m, 2H), 1.08-
1.03 (m, 2H). 13C NMR d: 143.1 (CH), 132.4, 131.2 (CH),
129.1 (CH), 128.5 (CH), 125.7 (CH), 31.4 (CH), 5.4 (CH2).
MS m/z: 209.3 [M þ H]þ (calcd for C11H13O2Sþ 209.1).
Acknowledgement
We gratefully acknowledge the Department of Henan Province Natural
Science and Technology Foundation (No. 172102210225), Natural
Science Foundation in Henan Province Department of Education (No.
17A150005, 17A150007), the Program for Innovative Research Team
from Zhengzhou (No. 131PCXTD605), and Project of Youth Backbone
Teachers of Henan University of Technology (No. 2016003).
(E)-1-Methoxy-4-[2-(benzenesulfonyl)vinyl]benzene (3bb)
Colorless solid, mp 200–201 ꢀC [lit.[62] mp 100–101 ꢀC]. IR:
3062, 2918, 2848, 1603, 1512, 1444, 1263, 1144, 1084. 1H
NMR d: 7.94 (d, JH-H ¼ 7.3 Hz, 2H), 7.65-7.58 (m, 2H), 7.53
(t, JH-H ¼ 7.8 Hz, 2H), 7.43 (d, JH-H ¼ 8.7 Hz, 2H), 6.89 (d,
JH-H ¼ 8.7 Hz, 2H), 6.71 (d, JH-H ¼ 15.3 Hz, 1H), 3.83 (s,
3H). 13C NMR d: 162.1, 142.3 (CH), 141.1, 133.2 (CH),
130.4 (CH), 129.3 (CH), 127.5 (CH), 124.9, 124.4 (CH),
114.5 (CH), 55.5 (CH3). MS m/z: 275.2 [M þ H]þ (calcd for
C15H15O3Sþ 275.1).
Disclosure statement
No potential conflict of interests was reported by the authors.
References
[1] Aziz, J.; Messaoudi, S.; Alami, M.; Hamze, A. Sulfinate
Derivatives: Dual and Versatile Partners in Organic Synthesis.
Org. Biomol. Chem. 2014, 12, 9743–9759. https://doi.org/10.
1039/C4OB01727G.
[2] Noshi, M. N.; El-Awa, A.; Torres, E.; Fuchs, P. L. Conversion
of Cyclic Vinyl Sulfones to Transposed Vinyl Phosphonates. J.
Am. Chem. Soc. 2007, 129, 11242–11247. https://doi.org/10.
1021/ja072890p.
(E)-1,2-Dimethoxy-4-[2-(benzenesulfonyl)vinyl] benzene
(3cb)
[3] Li, H.-M.; Song, J.; Liu, X.-F.; Deng, L.-J. Catalytic
Enantioselective C-C Bond Forming Conjugate Additions with
Vinyl Sulfones. J. Am. Chem. Soc. 2005, 127, 8948–8949.
https://doi.org/10.1021/ja0511063.
[4] Fang, Y.; Luo, Z.; Xu, X. Recent Advances in the Synthesis of
Vinyl Sulfones. RSC Adv. 2016, 6, 59661–59676. https://doi.
org/10.1039/C6RA10731A.
[5] Zhu, Q.; Lu, Y. Enantioselective Conjugate Addition of
Nitroalkanes to Vinyl Sulfone: An Organocatalytic Access to
Chiral Amines. Org. Lett. 2009, 11, 1721–1724. https://doi.org/
10.1021/ol9003349.
Colorless solid, mp 145–146 ꢀC [lit.[67] mp 153–154 ꢀC]. IR:
3047, 2935, 2844, 1610, 1510, 1464, 1271, 1142, 1024. 1H
NMR d: 7.95 (d, JH-H ¼ 7.3 Hz, 2H), 7.64-7.59 (m, 2H), 7.56-
7.52 (m, 2H), 7.09 (dd, JH-H ¼ 8.3 Hz, JH-H ¼ 1.9 Hz, 1H),
6.98 (d, JH-H ¼ 1.9 Hz, 1H), 6.86 (d, JH-H ¼ 8.3 Hz, 1H), 6.76
(d, JH-H ¼ 15.3 Hz, 1H), 3.90 (s, 3H), 3.87 (s, 3H). 13C NMR
(CDCl3) d: 151.8, 149.3, 142.6 (CH), 141.1, 133.2 (CH),
129.3 (CH), 127.5 (CH), 125.2, 124.6 (CH), 123.6 (CH),
111.0 (CH), 109.9 (CH), 56.0 (CH3), 55.9 (CH3). MS m/z:
304.0 [M þ H]þ (calcd for C16H16O4Sþ 304.1).
[6] Clive, D. L. J.; Li, Z.; Yu, M. Intramolecular Conjugate
Displacement:
A General Route to Hexahydroquinolizines,

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
7
Hexahydroindolizines, and Related [m,n,0]-Bicyclic Structures
with Nitrogen at Bridgehead. J. Org. Chem. 2007, 72,
5608–5617. https://doi.org/10.1021/jo070664s.
Methodology for the Synthesis of Unsaturated Aryl Sulfides and
Aryl Sulfones. J. Org. Chem. 1978, 43, 1208–1217. https://doi.
org/10.1021/jo00400a041.
a
[7] Wardrop, D. J.; Fritz, J. Total Synthesis of ( )-Magnofargesin. [23] van Steenis, J. H.; van Es, J. J. G. S.; van der Gen, A.
Org. Lett. 2006, 8, 3659–3662. https://doi.org/10.1021/ol0609053.
Stereoselective Synthesis of (E)-Vinyl Sulfoxides by the Horner-
Wittig Reaction. Eur. J. Org. Chem. 2000, 2000, 2787–2793.
https://doi.org/10.1002/1099-0690(200008)2000:15 < 2787:AID-
EJOC2787 > 3.0.CO;2-Z.
ꢀ
ꢀ
ꢀ
[8] Lopez-Perez, A.; Robles-Machın, R.; Adrio, J.; Carretero, J. C.
Oligopyrrole Synthesis by 1,3-Dipolar Cycloaddition of
Azomethine Ylides with Bis-sulfonyl Ethylenes. Angew. Chem. Int.
Ed. 2007, 46, 9261–9264. https://doi.org/10.1002/anie.200703258.
[9] Padwa, A.; Lipka, H.; Watterson, S. H.; Murphree, S. S.
Phenylsulfonyl Ene-Allenes as Efficient Precursors to Bicyclic
Synthesis via Intramolecular [2 þ 2]-Cycloaddition Reactions. J.
[24] Xue, Q.; Mao, Z.; Shi, Y.; Mao, H.; Cheng, Y.; Zhu, C. Metal-
Free, One-Pot Highly Selective Synthesis of (E)-Vinyl Sulfones
and Sulfoxides via Addition-Oxidation of Thiols with Alkynes.
Tetrahedron Lett. 2012, 53, 1851–1854. https://doi.org/10.1016/
j.tetlet.2012.01.135.
Org. Chem. 2003, 68, 6238–6250.
https://doi.org/10.1021/
ꢀ
€
€
jo0345796.
[25] Linden, A. A.; Kruger, L.; Backvall, J. Highly Selective
Sulfoxidation of Allylic and Vinylic Sulfides by Hydrogen
Peroxide Using a Flavin as Catalyst. J. Org. Chem. 2003, 68,
5890–5896. https://doi.org/10.1021/jo034273z.
[10] Carr, R. V. C.; Paquette, L. A. An Ethylene and Terminal
Olefin Equivalent in [4 þ 2]p Cycloadditions. General Synthetic
Application of Phenyl Vinyl Sulfone to the Construction of
Functionalized Six-Membered Rings. J. Am. Chem. Soc. 1980, [26] Reeves, D. C.; Rodriguez, S.; Lee, H.; Haddad, N.;
102, 853–855. https://doi.org/10.1021/ja00522a075.
Krishnamurthy, D.; Senanayake, C. H. Palladium-Catalyzed
Coupling of Vinyl Tosylates with Arylsulfinate Salts.
Tetrahedron Lett. 2009, 50, 2870–2873. https://doi.org/10.1016/
j.tetlet.2009.03.174.
[11] Steert, K.; El-Sayed, I.; Van der Veken, P.; Krishtal, A.; Van
Alsenoy, C.; Westrop, G. D.; Mottram, J. C.; Coombs, G. H.;
Augustyns, K.; Haemers, A. Dipeptidyl a-Fluorovinyl Michael
Acceptors: Synthesis and Activity against Cysteine Proteases. [27] Huang, F.; Batey, R. A. Cross-Coupling of Organoboronic
Bioorg. Med. Chem. Lett. 2007, 17, 6563–6566. https://doi.org/
10.1016/j.bmcl.2007.09.075.
[12] Uttamchandani, M.; Liu, K.; Panicker, R. C.; Yao, S. Q.
Activity-based Fingerprinting and Inhibitor Discovery of
Acids and Sulfinate Salts Using Catalytic Copper(II) Acetate
and 1, 10-Phenanthroline: Synthesis of Aryl and
Alkenylsulfones. Tetrahedron 2007, 63, 7667–7672. https://doi.
org/10.1016/j.tet.2007.05.029.
Cysteine Proteases in a Microarray. Chem. Commun. 2007, 0, [28] Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M.; Bernini, R.
1518–1520. https://doi.org/10.1039/B702826A.
Unsymmetrical Diaryl Sulfones and Aryl Vinyl Sulfones
through Palladium-Catalyzed Coupling of Aryl and Vinyl
Halides or Triflates with Sulfinic Acid Salts. J. Org. Chem. 2004,
69, 5608–5614. https://doi.org/10.1021/jo0493469.
[13] Reddick, J. J.; Cheng, J.; Roush, W. R. Relative Rates of Michael
Reactions of 20-(Phenethyl)thiol with Vinyl Sulfones, Vinyl
Sulfonate Esters, and Vinyl Sulfonamides Relevant to Vinyl
Sulfonyl Cysteine Protease Inhibitors. Org. Lett. 2003, 5, [29] Kabalka, G. W.; Guchhait, S. K. Convenient Synthesis of
1967–1970. https://doi.org/10.1021/ol034555l.
a,b-Unsaturated Sulfones via a Mizoroki-Heck Reaction of
Arylboronic Acids with Phenyl Vinyl Sulfones. Tetrahedron
Lett. 2004, 45, 4021–4022. https://doi.org/10.1016/j.tetlet.2004.
03.179.
[14] Palmer, J. T.; Rasnick, D.; Klaus, J. L.; Br€omme, D. Vinyl
Sulfones as Mechanism-Based Cysteine Protease Inhibitors. J.
Med. Chem. 1995, 38, 3193–3196. https://doi.org/10.1021/
jm00017a002.
[15] Meadows, D. C.; Sanchez, T.; Neamati, N.; North, T. W.;
Gervay-Hague, J. Ring Substituent Effects on Biological Activity
of Vinyl Sulfones as Inhibitors of HIV-I. Bioorg. Med. Chem.
2007, 15, 1127–1137. https://doi.org/10.1016/j.bmc.2006.10.017.
[30] Kirihara, M.; Yamamoto, J.; Noguchi, T.; Hirai, Y. Selective
Synthesis of Sulfoxides and Sulfones by Tantalum(V) Catalyzed
Oxidation of Sulfides with 30% Hydrogen Peroxide.
Tetrahedron Lett. 2009, 50, 1180–1183. https://doi.org/10.1016/
j.tetlet.2008.12.064.
[16] Frankel, B. A.; Bentley, M.; Kruger, R. G.; McCafferty, D. G. [31] Wang, L.; Yue, H.; Yang, D.; Cui, H.; Zhu, M.; Wang, J.; Wei,
Vinyl Sulfones: Inhibitors of SrtA, a Transpeptidase Required
for Cell Wall Protein Anchoring and Virulence in
Staphylococcus Aureus. J. Am. Chem. Soc. 2004, 126, 3404–3405.
https://doi.org/10.1021/ja0390294.
W.; Wang, H. Metal-Free Oxidative Coupling of Aromatic
Alkenes with Thiols Leading to (E)-Vinyl Sulfones. J. Org.
Chem. 2017, 82, 6857–6864. https://doi.org/10.1021/acs.joc.
7b00994.
[17] Kudryavtsev, K. V.; Bentley, M. L.; McCafferty, D. G. Probing [32] Cai, S.; Xu, Y.; Chen, D.; Li, L.; Chen, Q.; Huang, M.; Weng,
of cis-5-Phenyl Proline Scaffold as a Platform for the Synthesis
of Mechanism-Based Inhibitors of the Staphylococcus Aureus
Sortase SrtA Isoform. Bioorg. Med. Chem. 2009, 17, 2886–2893.
https://doi.org/10.1016/j.bmc.2009.02.008.
W. Visible-Light-Enabled Decarboxylative Sulfonylation of
Cinnamic Acids with Sulfonylhydrazides under Transition-
Metal-Free Conditions. Org. Lett. 2016, 18, 2990–2993. https://
doi.org/10.1021/acs.orglett.6b01353.
[18] Singh, A.; Rosenthal, P. J. Positive Role of the Mammalian [33] Katrun, P.; Hlekhlai, S.; Meesin, J.; Pohmakotr, M.; Reutrakul,
TBPIP/HOP2 Protein in DMC1-Mediated Homologous Pairing.
J. Biol. Chem. 2004, 279, 35263–35272. https://doi.org/10.1074/
jbc.M402481200.
V.; Jaipetch, T.; Soorukram, D.; Kuhakarn, C. PhI(OAc)2
Mediated Decarboxylative Sulfonylation of b-Aryl-
a,b-unsaturated Carboxylic Acids: A Synthesis of (E)-Vinyl
Sulfones. Org. Biomol. Chem. 2015, 13, 4785–4794. https://doi.
org/10.1039/C5OB00417A.
[19] Liu, S.; Zhou, B.; Yang, H.; He, Y.; Jiang, Z. X.; Kumar, S.; Wu,
L.; Zhang, Z. Y. Aryl Vinyl Sulfonates and Sulfones as Active
Site-Directed and Mechanism-Based Probes for Protein [34] Rong, G.; Mao, J.; Yan, H.; Zheng, Y.; Zhang, G. Phosphoric
Tyrosine Phosphatases. J. Am. Chem. Soc. 2008, 130,
8251–8260. https://doi.org/10.1021/ja711125p.
[20] Chodroff, S.; Whitmore, W. F. The Preparation of Unsaturated
Sulfones by Condensation Reactions. J. Am. Chem. Soc. 1950,
72, 1073–1076. https://doi.org/10.1021/ja01159a005.
[21] Gancarz, R. A.; Kice, J. L. Photodecomposition of
Selenosulfonates and Their Facile Photoaddition to Alkenes.
Tetrahedron Lett. 1980, 21, 4155–4158. https://doi.org/10.1016/
S0040-4039(00)93676-1.
Acid-Mediated Synthesis of Vinyl Sulfones through
Decarboxylative Coupling Reactions of Sodium Sulfinates with
Phenylpropiolic Acids. J. Org. Chem. 2015, 80, 7652–7657.
https://doi.org/10.1021/acs.joc.5b01212.
[35] Singh, R.; Allam, B. K.; Singh, N.; Kumari, K.; Singh, S. K.;
Singh, K. N. A Direct Metal-Free Decarboxylative Sulfono
Functionalization (DSF) of Cinnamic Acids to a,b-unsaturated
Phenyl Sulfones. Org. Lett. 2015, 17, 2656–2659. https://doi.
org/10.1021/acs.orglett.5b01037.
[22] Hopkin, P. B.; Fuchs, P. L. Chlorosulfenylation- [36] Tang, S.; Wu, Y.; Liao, W.-Q.; Bai, R.-P.; Liu, C.; Lei, A.-W.
Dehydrochlorination Reactions. New and Improved Revealing the Metal-Like Behavior of Iodine: An Iodide-

8
G.-F. HONG ET AL.
Catalysed Radical Oxidative Alkenylation. Chem. Commun. [51] Wei, W.; Cui, H.; Yang, D.; Liu, X.; He, C.; Dai, S.; Wang, H.
2014, 50, 4496–4499. https://doi.org/10.1039/C4CC00644E.
[37] Li, X.-W.; Xu, Y.-L.; Jiang, C.; Qi, C.-R.; Jiang, H.-F.; Wu, W.
Copper-Catalyzed Aerobic Oxidative N-S Bond
Functionalization for C-S Bond Formation: Regio- and
Metal-free Molecular Iodine-catalyzed Direct Sulfonylation of
Pyrazolones with Sodium Sulfinates Leading to Sulfonated
Pyrazoles at Room Temperature. Org. Chem. Front. 2017, 4,
26–30.
Stereoselective Synthesis of Sulfones and Thioethers. Chem. Eur. [52] Wu, X.-S.; Chen, Y.; Li, M.-B.; Zhou, M.-G.; Tian, S.-K. Direct
J. 2014, 20, 7911–7915.
201402815.
[38] Rong, G.-W.; Mao, J.-C.; Yan, H.; Zheng, Y.; Zhang, G.-Q.
https://doi.org/10.1002/chem.
Substitution of Primary Allylic Amines with Sulfinate Salts. J.
Am. Chem. Soc. 2012, 134, 14694–14697. https://doi.org/10.
1021/ja306407x.
Iron/Copper Co-Catalyzed Synthesis of Vinyl Sulfones from [53] Maloney, K.; Kuethe, J.; Linn, K. A Practical, One-Pot Synthesis
Sulfonyl Hydrazides and Alkyne Derivatives. J. Org. Chem.
2015, 80, 4697–4703. https://doi.org/10.1021/acs.joc.5b00558.
of Sulfonylated Pyridines. Org. Lett. 2011, 13, 102–105. https://
doi.org/10.1021/ol102629c.
[39] Jiang, Y.-J.; Loh, T. P. Catalytic and Direct Methyl [54] Ueda, M.; Hartwig, J. F. Iridium-Catalyzed, Regio- and
Sulfonylation of Alkenes and Alkynes Using a Methyl Sulfonyl
Radical Generated from DMSO, Dioxygen and Copper
System. Chem. Sci. 2014, 5, 4939–4943. https://doi.org/10.1039/
C4SC01901F.
Enantioselective Allylic Substitution with Aromatic and
Aliphatic Sulfinates. Org. Lett. 2010, 12, 92–94. https://doi.org/
10.1021/ol9023248.
a
[55] Li, Y.; Cheng, K.; Lu, X.; Sun, J. A Facile and Efficient
Approach to N-Protected b-Sulfinyl-Enamines via C-
Sulfinylation of Enamides and Enecarbamates. Adv. Synth.
[40] Xu, Y.-L.; Zhao, J.-W.; Tang, X.-D.; Wu, W.-Q.; Jiang, H.-F.
Chemoselective Synthesis of Unsymmetrical Internal Alkynes or
Vinyl Sulfones via Palladium-Catalyzed Cross-Coupling
Reaction of Sodium Sulfinates with Alkynes. Adv. Synth. Catal.
2014, 356, 2029–2039. https://doi.org/10.1002/adsc.201300945.
[41] Xi, Y.; Dong, B.; McClain, E. J.; Wang, Q.; Gregg, T. L.;
Akhmedov, N. G.; Petersen, J. L.; Shi, X. Gold-Catalyzed
Intermolecular C-S Bond Formation: Efficient Synthesis of
a-Substituted Vinyl Sulfones. Angew. Chem. Int. Ed. 2014, 53,
4657–4661. https://doi.org/10.1002/ange.201310142.
Catal. 2010, 352, 1876–1880.
https://doi.org/10.1002/adsc.
201000084.
[56] Katrun, P.; Chiampanichayakul, S.; Korworapan, K.;
Pohmakotr, M.; Reutrakul, V.; Jaipetch, T.; Kuhakarn, C.
Ph(OAc)2/KI-Mediated Reaction of Aryl Sulfinates with
Alkenes, Alkynes, and a,b-Unsaturated Carbonyl Compounds:
Synthesis of Vinyl Sulfones and b-Iodovinyl Sulfones. Eur. J.
Org. Chem. 2010, 2010, 5633–5641. https://doi.org/10.1002/
ejoc.201000641.
[42] Wei, W.; Li, J.; Yang, D.; Wen, J.; Jiao, Y.; You, J.; Wang, H.
Copper-Catalyzed Highly Selective Direct Hydrosulfonylation of [57] Zhang, N.; Yang, D.; Wei, W.; Yuan, L.; Cao, Y.; Wang, H.
Alkynes with Arylsulfinic Acids Leading to Vinyl Sulfones. Org.
Biomol. Chem. 2014, 12, 1861–1864. https://doi.org/10.1039/
C3OB42522C.
Metal-Free Iodine-Mediated Synthesis of Vinyl Sulfones at
Room Temperature Using Water as Solvent. RSC Adv. 2015, 5,
37013–37017. https://doi.org/10.1039/C5RA02927A.
[43] Zhao, Y.; Lai, Y.-L.; Du, K.-S.; Lin, D.-Z.; Huang, J.-M. [58] Taniguchi, N. Stereoselective Synthesis of (E)-Alkene Sulfones
Electrochemical Decarboxylative Sulfonylation of Cinnamic
Acids with Aromatic Sulfonylhydrazides to Vinyl Sulfones. J.
Org. Chem. 2017, 82, 9655–9661. https://doi.org/10.1021/acs.
joc.7b01741.
from Alkenes or Alkynes via Copper-Catalyzed Oxidation of
Sodium Sulfinates. Synlett. 2011, 2011, 1308–1312. https://doi.
org/10.1055/s-0030-1260544.
[59] Nair, V.; Augustine, A.; Suja, T. D. CAN Mediated Reaction of
Aryl Sulfinates with Alkenes and Alkynes: Synthesis of Vinyl
Sulfones, b-Iodovinyl Sulfones and Acetylenic Sulfones.
Synthesis 2002, 2002, 2259–2265. https://doi.org/10.1055/s-
2002-34838.
[44] Lin, Y.; Lu, G.; Wang, G.; Yi, W. Odorless, Regioselective
Synthesis of Diaryl Sulfides and a-Thioaryl Carbonyls from
Sodium Arylsulfinates via a Metal-Free Radical Strategy in
Water. Adv. Synth. Catal. 2016, 358, 4100–4105. https://doi.
org/10.1002/adsc.201600846.
[45] Lin, Y.; Lu, G.; Wang, G.; Yi, W. Acid/Phosphide-Induced
Radical Route to Alkyl and Alkenyl Sulfides and
Phosphonothioates from Sodium Arylsulfinates in Water. J.
€
€
[60] Meyer, A. U.; Jager, S.; Hari, D. P.; Konig, B. Visible Light-
Mediated Metal-Free Synthesis of Vinyl Sulfones from Aryl
Sulfinates. Adv. Synth. Catal. 2015, 357, 2050–2054. https://doi.
org/10.1002/adsc.201500142.
Org. Chem. 2017, 82, 382–389. https://doi.org/10.1021/acs.joc. [61] Luo, Y.-C.; Pan, X.-J.; Yuan, G.-Q. An Efficient Electrochemical
6b02459.
Synthesis of Vinyl Sulfones from Sodium Sulfinates and
Olefins. Tetrahedron 2015, 71, 2119–2123. https://doi.org/10.
1016/j.tet.2015.02.048.
[46] Lin, Y.; Lu, G.; Cai, C.; Yi, W. Odorless, One-Pot Regio- and
Stereoselective Iodothiolation of Alkynes with Sodium
Arenesulfinates under Metal-Free Conditions in Water. Org. [62] Qian, P.; Bi, M.; Su, J.; Zha, Z.; Wang, Z. Electrosynthesis of
Lett. 2015, 17, 3310–3313. https://doi.org/10.1021/acs.orglett.
5b01488.
[47] Xiao, F.; Chen, S.; Tian, J.; Huang, H.; Liu, Y.; Deng, G.
Chemoselective Cross-Coupling Reaction of Sodium Sulfinates
(E)-Alkene Sulfones Directly from Cinnamic Acids and Sodium
Sulfinates via Decarboxylative Sulfono Functionalization. J. Org.
Chem. 2016, 81, 4876–4882. https://doi.org/10.1021/acs.joc.
6b00661.
with Phenols under Aqueous Conditions. Green Chem. 2016, [63] Guo, R.; Gui, Q.; Wang, D.; Tan, Z. Synthesis of Vinysulfones
18, 1538–1546. https://doi.org/10.1039/C5GC02292D.
[48] Wei, W.; Cui, H.; Yang, D.; Yue, H.; He, C.; Zhang, Y.; Wang,
H. Visible-Light-Enabled Spirocyclization of Alkynes Leading to
3-Sulfonyl and 3-Sulfenyl Azaspiro[4,5]trienones. Green Chem.
2017, 19, 5608–5613. https://doi.org/10.1039/C7GC02330H.
[49] Wei, W.; Wen, J.; Yang, D.; Jing, H.; You, J.; Wang, H. Direct
Difunctionalization of Alkynes with Sulfinic Acids and
Molecular Iodine: A Simple and Convenient Approach to (E)-
via Palladium-catalyzed Decarboxylative Coupling of Cinnamic
Acids with Aromatic Sulfinic Acid Sodium Salts. Catal. Lett.
2014, 144, 1377–1383.
https://doi.org/10.1007/s10562-014-
1286-5.
[64] Gao, J.; Lai, J.; Yuan, G. Iodine-Mediated Synthesis of (E)-
Alkene Sulfones from Sodium Sulfinates and Cinnamic Acids in
Aqueous Medium. RSC Adv. 2015, 5, 66723–66726. https://doi.
org/10.1039/C5RA10896A.
b-Iodovinyl Sulfones. RSC Adv. 2015, 5, 4416–4419. https:// [65] Xu, Y.; Tang, X.; Hu, W.; Wu, W.; Jiang, H. Transition-Metal-
doi.org/10.1039/C4RA13998D.
Free Synthesis of Vinyl Sulfones via Tandem Cross-decarboxy-
lative/Coupling Reactions of Sodium Sulfinates and Cinnamic
Acids. Green Chem. 2014, 16, 3720–3723. https://doi.org/10.
1039/C4GC00542B.
[50] Wei, W.; Wen, J.; Yang, D.; Du, J.; You, J.; Wang, H. Catalyst-
Free Direct Arylsulfonylation of N-Arylacrylamides with
Sulfinic Acids: A Convenient and Efficient Route to Sulfonated
Oxindoles. Green Chem. 2014, 16, 2988–2991. https://doi.org/ [66] Jiang, Q.; Xu, B.; Jia, J.; Zhao, A.; Zhao, Y.-R.; Li, Y.-Y.; He, N.-
10.1039/C4GC00231H. N.; Guo, C.-C. Copper-Catalyzed Aerobic Decarboxylative

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
9
Sulfonylation of Cinnamic Acids with Sodium Sulfinates: [74] Das, B.; Lingaiah, M.; Damodar, K.; Bhunia, N. An Efficient
Synthesis of Vinyl Sulfones from Alkenes and Aryl Sulfinates.
Synthesis 2011, 2011, 2941–2944. https://doi.org/10.1055/s-
0030-1260142.
Stereospecific Synthesis of (E)-Alkene Sulfones. J. Org. Chem.
2014, 79, 7372–7379. https://doi.org/10.1021/jo5010845.
[67] Chen, J.; Mao, J.; Zheng, Y.; Liu, D.; Rong, G.; Yan, H.; Zhang,
C.; Shi, D. Iodine-Promoted Decarboxylative C-S Cross-
Coupling of Cinnamic Acids with Sodium Benzene Sulfinates.
Tetrahedron 2015, 71, 5059–5063. https://doi.org/10.1016/j.tet.
2015.05.115.
[68] Jang, Y.-J.; Yan, M.-C.; Lin, Y.-F.; Yao, C.-F. A Simple Radical
Addition-Elimination Route to Geometrically Pure (E)-Alkene
and Chromanone Derivatives via b-Nitrostyrenes. J. Org. Chem.
2004, 69, 3961–3963. https://doi.org/10.1021/jo049763l.
[69] Jang, Y.-J.; Liu, J.-Y.; Kuo, W.-Y.; Yao, C.-F. Improved One-Pot
Synthesis of Styryl Tetrahydrofurans and Cyclohexanes by
Radical Addition to b-Nitrostyrenes in the Presence of Benzoyl
Peroxide. Chem. Eur. J. 2003, 9, 2123–2128. https://doi.org/10.
1002/chem.200204571.
[75] Nair, V.; Augustine, A.; George, T. G.; Nair, L. G. An Efficient
One-Pot Synthesis of Vinyl Sulphones via CAN Mediated
Reaction of Aryl Sulphinates and Alkenes. Tetrahedron Lett.
2001,
42,
6763–6765.
https://doi.org/10.1016/S0040-
4039(01)01377-6.
[76] Lu, Q.; Zhang, J.; Wei, F.; Qi, Y.; Wang, H.; Liu, Z.; Lei, A.
Aerobic Oxysulfonylation of Alkenes Leading to Secondary and
Tertiary b-Hydroxysulfones. Angew. Chem. Int. Ed. 2013, 52,
7156–7259. https://doi.org/10.1002/ange.201301634.
[77] Lu, Q.; Zhang, J.; Zhao, G.; Qi, Y.; Wang, H.; Lei, A. Dioxygen-
Triggered Oxidative Radical Reaction: Direct Aerobic
Difunctionalization of Terminal Alkynes toward b-keto
Sulfones. J. Am. Chem. Soc. 2013, 135, 11481–11484. https://
doi.org/10.1021/ja4052685.
[70] Liu, J. T.; Jang, Y. J.; Shih, Y. K.; Hu, S. R.; Chu, C. M.; Yao, C. F.
Novel Synthesis of Alkenes via Triethylborane-Induced Free-
Radical Reactions of Alkyl Iodides and b-Nitrostyrenes. J. Org.
Chem. 2001, 66, 6021–6028. https://doi.org/10.1021/jo010213m.
[71] Yao, C. F.; Chu, C. M.; Liu, J. T. Free-Radical Reactions of
Trialkylboranes with b-Nitrostyrenes to Generate Alkenes. J. Org.
Chem. 1998, 63, 719–722. https://doi.org/10.1021/jo9716901.
[72] Keshari, T.; Kapoorr, R.; Yadav, L. D. S. Silver-Catalyzed
[78] Liu, X.-T.; Ding, Z.-C.; Ju, L.-C.; Xu, S.-X.; Zhan, Z.-P.
Copper(II)-Catalyzed Chemo- and Stereocontrolled Synthesis of
(E)-Viinyl Sulfones and (Z)-b-Chlorovinyl Sulfones from
Terminal Alkynes and Arylsulfonyl Hydrazides. Synthesis 2017,
49, 1575–1582. https://doi.org/10.1055/s-0036-1588918.
[79] Lin, Y.-M.; Lu, G.-P.; Wang, R.-K.; Yi, W.-B. Stereoselective
Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and
Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl
Sulfides. Org. Lett. 2017, 19, 1100–1103. https://doi.org/10.
1021/acs.orglett.7b00126.
[80] Xu, Y.-L.; Zhao, J.-W.; Tang, X.-D.; Wu, W.-Q.; Jiang, H.-F.
Chemoselective Synthesis of Unsymmetrical Internal Alkynes or
Vinyl Sulfones via Palladium-catalyzed Cross-coupling Reaction
of Sodium Sulfinates with Alkynes. Adv. Synth. Cat. 2014, 356,
2029–2039. https://doi.org/10.1002/adsc.201300945.
Denitrative Sulfonylation of b-Nitrostyrenes:
A Convenient
Approach to (E)-vinyl Sulfones. Eur. J. Org. Chem. 2016, 2016,
2695–2699. https://doi.org/10.1002/ejoc.201600237.
[73] Nie, G.; Deng, X.; Lei, X.; Hu, Q.; Chen, Y. Mn(III)-Mediated
Regioselective Synthesis of (E)-Vinyl Sulfones from Sodium
Sulfinates and Nitro-Olefins. RSC Adv. 2016, 6, 75277–75281.
https://doi.org/10.1039/C6RA17842A.