Synthesis of vinyl sulfones through sulfonylation of styrenes with sulfonyl chlorides under metal-free conditions

Article abstract of DOI:10.1016/j.tet.2020.131082

A hypervalent iodine reagent-mediated sulfonylation of styrenes with sulfonyl chlorides was developed for the synthesis of vinyl sulfones. The reaction proceeded under metal-free, mild and neutral conditions without extra oxidants or bases. It also exhibited good air and moisture tolerance, broad substrate scope and high chemo-selectivity, affording the vinyl sulfones in moderate to good yields.

Full text of DOI:10.1016/j.tet.2020.131082

Journal Pre-proof
Synthesis of vinyl sulfones through sulfonylation of styrenes with sulfonyl chlorides
under metal-free conditions
Xia Wang, Bo Hu, Peng Yang, Qian Zhang, Dong Li
PII:
S0040-4020(20)30203-9
https://doi.org/10.1016/j.tet.2020.131082
TET 131082
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 16 December 2019
Revised Date: 31 January 2020
Accepted Date: 24 February 2020
Please cite this article as: Wang X, Hu B, Yang P, Zhang Q, Li D, Synthesis of vinyl sulfones through
sulfonylation of styrenes with sulfonyl chlorides under metal-free conditions, Tetrahedron (2020), doi:
https://doi.org/10.1016/j.tet.2020.131082.
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Synthesis of vinyl sulfones through sulfonylation of
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Xia Wang, Bo Hu, Peng Yang, Qian Zhang*, Dong Li*
School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China

Tetrahedron
journal homepage: www.elsevier.com
Synthesis of vinyl sulfones through sulfonylation of styrenes with sulfonyl
chlorides under metal-free conditions
Xia Wang a, Bo Hu a, Peng Yang a, Qian Zhang a*, Dong Li a,
aSchool of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A hypervalent iodine reagent-mediated sulfonylation of styrenes with sulfonyl chlorides was
developed for the synthesis of vinyl sulfones. The reaction proceeded under metal-free, mild and
neutral conditions without extra oxidants or bases. It also exhibited good air and moisture
tolerance, broad substrate scope and high chemo-selectivity, affording the vinyl sulfones in
moderate to good yields.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Vinyl sulfone
Hypervalent iodine
Sulfonylation
Styrene
Sulfonyl chloride
induced sulfonylation of styrenes with sulfonate esters.8 Very
recently, Mal and coworkers reported an N-iodosuccinimide-
mediated sulfonylation of styrenes with sulfonyl hydrazides.9
However, most of these methods still required a strong oxidant
like TBHP or extra bases (Scheme 1b). More concise and milder
reaction conditions are still demanded. On the other hand,
sulfonyl chloride is a preferable sulfonylation reagent due to its
high stability, ready availability and easy handling.
1. Introduction
Sulfur-containing compound is of great importance as it finds
widespread utilization in various fields of organic, biological and
materials chemistry.1 Among them, vinyl sulfones are versatile
building blocks and convenient intermediates in organic
synthesis and also important moieties in many natural products
and biologically active compounds.2 Classical methods to
synthesize vinyl sulfones are mainly based on condensation,
olefination or transition-metal-catalyzed cross coupling
reactions.3 Alkenes are among the most basic and cheap starting
materials in organic synthesis. Thus direct sulfonylation of
alkenes emerged as a more powerful and efficient method for
preparation of vinyl sulfones. Kimigata and coworkers first
reported a ruthenium-catalyzed sulfonylation of styrenes with
sulfonyl chlorides in 1983.4 In the past decade, the
transformations under copper, silver or photoredox catalysis
were also accomplished.5 However, these sulfonylation methods
required the involvement of metal catalysts, and sometimes also
expensive ligands, extra stoichiometric oxidants or bases
(Scheme 1a). In this regard, synthesis methods for vinyl sulfones
under metal-free conditions are considerably desired on account
of sustainable and green chemistry.6
Scheme 1. Synthesis of vinyl sulfones from styrenes
Efforts have also been devoted to metal-free sulfonylation of
alkenes in recent years. It was mainly achieved through
sulfonylation using sulfonyl hydrazides or sodium sulfinates
under iodine, hypervalent iodine or photoredox catalysis.7 For a
Hypervalent iodine reagents have attracted much attention in
organic synthesis as easily accessible, stable, efficient and
environmentally benign oxidants in recent years.10 Significant
progress has also been made in hypervalent iodine reagents-
recent instance, Gevorgyan and coworkers developed a light-
———
Corresponding author. E-mails: zhangqian620@hotmail.com (Q. Zhang);dongli@mail.hbut.edu.cn (D. Li)

2
Tetrahedron
promoted selective C−H bond functionalization under metal-free
conditions.11 In 2015 Kuhakarn and coworkers reported a
hypervalent
iodine
reagent-mediated
decarboxylative
sulfonylation of β-aryl-α,β-unsaturated carboxylic acids with
sodium sulfinates for the preparation of vinyl sulfones.12 In
2016, our group developed a hypervalent iodine reagent-
mediated site-selective oxidative C–H sulfonylation of 8-
amidoquinolines and anilides with sulfonyl chlorides.13 Along
with our study on the hypervalent iodine chemistry,14 herein we
report the hypervalent iodine reagent-mediated sulfonylation of
styrenes with sulfonyl chlorides under metal-free conditions,
which provided a novel method for the synthesis of vinyl
sulfones (Scheme 1c).
Fugure 1. X-ray crystallography of 3a
Under the optimized conditions, the substrate scope of
styrenes (1) with TsCl (2a) was explored as shown in Table 2.
It's pleasant to find that good functional group compatibility was
demonstrated for a variety of styrenes on the phenyl group such
as alkoxyl, F, Br, and CF3. The desired vinyl sulfone products
were obtained in moderate to good yields (3b–3k). Electronic
effect was observed in this reaction that the electron-rich styrene
(3b and 3c) gave higher yields than the electron-poor substrates
(3g–3k). Substrates with a substituent on ortho-, meta- or para-
position gave similar results without significant steric hindrance
effect (3e and 3f, 3h–3j). Notably, 1,1-diphenylethylene could
also provide 47% yield of desired product (3l). However, when
p-tert-butylstyrene was used the vinyl sulfone product was not
obtained. Instead, a β-chlorosulfone 3m’ was isolated in 57%
yield through chlorosulfonylation of the double bond.
2. Results and discussion
Initial study was carried out with 4-methoxystyrene (1a) (0.2
mmol) and TsCl (2a) (0.4 mmol) as the model reaction and the
results were summarized in Table 1. The sulfonylation occurred
in the presence of 2 equivalents of PhI(OAc)2 (0.4 mmol) in
THF at 80 °C for 12 h which produced the desired product (3a)
in 50% yield (entry 1). The structure of 3a was unambiguously
confirmed by X-ray crystallography (Figure 1).15 Other solvents
such as CH3CN, DCM, toluene, chlorobenzene, and DCE were
subsequently examined but did not provide better results than
THF (entries 2–6). Then other hypervalent iodine reagents were
tested in THF. The employment of PhIO and PhI(OTFA)2
resulted in no reaction (entries 7 and 8). PhI(OPiv)2 provided
similar product yield as PhI(OAc)2 (entry 9). Notably a better
result (65% yield) was obtained using PhI(OCOPh)2 (entries 10).
The reactions under reduced or elevated temperatures were
investigated but no improvement was observed (entries 11–13).
Shortening the reaction time to 8 h resulted in a lower yield but
prolonging the reaction time to 16 h afforded the product in 71%
yield (entries 14 and 15). Further prolonging the reaction time to
24 h did not give better result (entry 16). Thus the conditions
showed in entry 15 were chose as the best one and subsequently
applied to explore the scope of this reaction.
The substrate scope of other sulfonyl chlorides (2) was
investigated subsequently as shown in Table 3. Benzenesulfonyl
chloride reacted with 4-methoxystyrene (1a) to give the vinyl
sulfone 3n in 67% yield. The o-tosyl chloride also underwent the
reaction smoothly to provide 85% product yield without
influence of steric hindrance effect (3o). Other functional groups
such as MeO, F, Cl and Br were also tolerated on the sulfonyl
Table 2. Substrate scope of styrenes (1)a,b
Table 1. Optimization of reaction conditionsa,b
T
(°C)
80
80
80
80
80
80
80
80
80
80
40
60
100
80
80
80
Yield
(%)b
50
11
20
10
10
0
Entry
Oxidant
Solvent
1
2
3
4
5
6
7
8
9
10
11
12
13
14c
15d
16e
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
THF
CH3CN
DCM
PhCl
toluene
DCE
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
PhI(OAc)2
PhIO
0
0
PhI(OTFA)2
PhI(OPiv)2
PhI(OCOPh)2
PhI(OCOPh)2
PhI(OCOPh)2
PhI(OCOPh)2
PhI(OCOPh)2
PhI(OOCPh)2
PhI(OCOPh)2
51
65
15
54
47
50
71
52
aReaction conditions: styrene (1) (0.2 mmol), 4-tolysufonyl chloride (2a)
(0.4 mmol), PhI(OCOPh)2 (0.4 mmol) in THF (2.0 mL) stirring at 80 °C
under air for 16 h. bIsolated yield; cPhI(OAc)2 (0.4 mmol) is used.
aReaction conditions: 4-methoxylstyrene (1a) (0.2 mmol), 4-tolysufonyl
chloride (2a) (0.4 mmol), oxidant (0.4 mmol) in solvent (2.0 mL) stirring
under air for 12 h. bIsolated yield. Reaction time 8 h. dReaction time 16 h.
c
eReaction time 24 h.

Table 3. Substrate scope of sulfonyl chlorides (2)a,b
SO2R
PhI(OCOPh) (2 eq)
R
R
+
RSO2Cl
THF, 80 C,16 h
1
2
3
Scheme 2. Gram-scale synthesis and control experiments.
Scheme 3. Inapplicable substrates
aReaction conditions: styrene (1) (0.2 mmol), sufonyl chloride (2) (0.4
mmol), PhI(OCOPh)2 (0.4 mmol) in THF (2.0 mL) stirring at 80 °C under
air for 16 h. bIsolated yield.
Based on these results and previous reports, a plausible
mechanism for this sulfonylation was proposed in Scheme 4. In
the presence of hypervalent iodine reagent, the sulfonyl chloride
converted to
a
sulfonyl radical.17 The sulfonyl radical
chlorides and the desired products were obtained in moderate to
good yields (3p–3r, 3u and 3v). Notably, the alkyl and 2-thienyl
sulfonyl chloride were also applicable in this protocol and gave
the desired products in yields of 55% and 90% respectively (3s
and 3t).
subsequently added to the styrene (1) to form a carbon-centered
radical A. Electron-rich styrenes were more reactive towards the
sulfonyl radical. Then intermediate A was trapped by chlorine
radical from homolytic cleavage of sulfonyl chloride to form the
chlorosulfonylation product 3’. Then, in some cases (for
instance if R1 is tert-butyl), 3’ was more stable than the
corresponding vinyl sulfones and did not proceed elimination
reaction under the reaction conditions stable which can be
isolated as the product (3m’). In other cases, elimination of HCl
from 3’ generated the vinyl sulfone products 3.
We also carried out the standard reaction in gram-scale to
examine the application potential of this method. With 10 mmol
(1.34 g) substrate 1a in 100 mL THF, the sulfonylation
proceeded smoothly to give the product in 70% yield (Scheme
2a). Control experiments were conducted for clarification of the
reaction mechanism. The sulfonylation of 1a and 2a in the
presence of
a
radical scavenger 2,2,6,6-tetramethyl-1-
piperidinyloxy (TEMPO) or butylated hydroxytoluene (BHT)
gave no desired products although no radical trapping product
was detected either (Scheme 2b). But a proton scavenger 2,6-di-
tert-butylpyridine (dtbpy) exhibited little influence to this
reaction (Scheme 2c). It implied that the reaction proceeded
through a radical mechanism. The study of possible reaction
intermediate was also conducted.
A pre-synthesized β-
chlorosulfone 3a’ was handled under standard conditions which
converted to the vinyl sulfone 3a in 65% yield (Scheme 2d).16
But the same treatment of 3m’ did not produce the vinyl sulfone
product 3m (Scheme 2e). It indicated the formation of a
chlorosulfonylation intermediate in this process which might
convert to the final product or remain unchangebly under
reaction conditions.
Scheme 4. Plausible reaction mechanism
Furthermore, some other styrene derivatives were also
examined and found to be inapplicable in this method (Scheme
3). The 2-phenyl-propene (4) only gave trace amount of product.
And 1-phenyl-propene (5) and allylbenzene (6) both resulted in
no reaction.

4
Tetrahedron
HRMS-ESI(m/z): calcd for C19H23O3S (M+H+): 330.1368, found
330.1370.
3. Conclusions
In summary, we have developed a hypervalent iodine
reagent-mediated sulfonylation of styrenes with sulfonyl
chlorides. The reaction proceeded under metal-free, mild and
neutral conditions and showed good air and moisture tolerance.
Broad substrate scope and high chemo-selectivity were
exhibited which afford the vinyl sulfones in moderate to good
yields. It provides a novel and facile strategy for synthesis of
vinyl sulfones.
4.3.4.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3d). Light
yellow solid, mp 90–92 °C; 1H NMR (400 MHz, CDCl3): δ 2.44
(s, 3H), 6.85 (d, J = 15.40 Hz, 1H), 7.35 (d, J = 8.12 Hz, 2H),
7.38–7.41 (m, 3H), 7.47–7.49 (m, 2H), 7.66 (d, J = 15.44 Hz,
1H), 7.83 (d, J = 8.24 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ
21.62, 127.63, 127.72, 128.53, 129.07, 129.97, 131.11, 132.46,
137.74, 141.95, 144.40. HRMS-ESI(m/z): calcd for C15H15O2S
(M+H+): 259.0793, found 259.0794.
4. Experimental section
4.3.5.
(E)-1-Methyl-2-(2-tosylvinyl)benzene
(3e).
Light
4.1. General experimental
yellow solid, mp 62–65 °C; 1H NMR (400 MHz, CDCl3): δ 2.44
(s, 3H), 2.46 (s, 3H), 6.77 (d, J = 15.28 Hz, 1H), 7.19–7.23 (m,
2H), 7.28–7.30 (m, 1H), 7.35 (d, J = 7.96 Hz, 2H), 7.42–7.44
(m, 1H), 7.82–7.85 (m, 2H) 7.94 (d, J = 15.32 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ 19.80, 21.64, 126.45, 126.80,
127.70, 128.39, 129.97, 130.84, 131.02, 131.29, 137.64, 138.15,
139.58, 144.37. HRMS-ESI(m/z): calcd for C16H17O2S (M+H+):
273.0949, found 273.0948.
1H NMR, 13C NMR and 19F NMR spectra were recorded on a
Bruker DPX-400 spectrometer with CDCl3 as the solvent and
TMS as an internal standard, operating at 400 MHz for 1H NMR,
100 MHz for 13C NMR and 376 MHz for 19F NMR. Melting
points were measured by SGW X-4A microscopic apparatus.
The X-ray crystallography was measured on Bruker D8
VENTURE PHOTON instrument. HRMS was measured by Q
Exactive LC/HRMS spectrometer. Ethyl acetate and hexane
were used for column chromatography without further
purification. All solvents and chemicals were obtained from
commercial sources and used as received unless otherwise noted.
4.3.6.
(E)-1-Methyl-3-(2-tosylvinyl)benzene (3f). Light yellow
solid, mp 74–76 °C; 1H NMR (400 MHz, CDCl3): δ 2.35 (s, 3H),
2.43 (s, 3H), 6.83 (d, J = 15.40 Hz, 1H), 7.27–7.28 (m, 3H), 7.34
(d, J = 8.00 Hz, 2H), 7.39 (d, J = 8.28 Hz, 1H), 7.63 (d, J =
15.40 Hz, 1H) 7.82 (d, J = 8.28 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 21.27, 21.63, 124.34, 125.76, 127.22, 127.66, 127.91,
128.92, 129.09, 129.94, 131.94, 138.79, 142.12, 144.34. HRMS-
ESI(m/z): calcd for C16H17O2S (M+H+): 273.0949, found
273.0946.
4.2. General procedure for the sulfonylation of styrenes (1).
A mixture of styrene (1, 0.2 mmol), sulfonyl chloride (2, 0.4
mmol), PhI(OOCPh)2 (0.4mmol) were added into a vial
containing a stirring bar and sealed with a Teflon-lined cap.
Then THF (2 mL) was introduced. The resulting mixture was
stirred at 80 °C for 16 h. Then the mixture was added into H2O
(25 mL) and extracted with ethyl acetate (10 mL) for three times.
The combined organic layer was dried over anhydrous MgSO4
and filtered. After removal of the solvent in vacuo, the residue
was purified by column chromatography (ethyl acetate/hexane)
to afford the pure product.
4.3.7.
(E)-1-Fluoro-4-(2-tosylvinyl)benzene (3g). White solid,
1
mp 79–80 °C; H NMR (400 MHz, CDCl3): δ 2.44 (s, 3H), 6.78
(d, J = 15.40 Hz, 1H), 7.05–7.11 (m, 2H), 7.35 (d, J = 8.04 Hz,
2H), 7.45–7.50 (m, 2H), 7.62 (d, J = 15.40 Hz, 1H), 7.81–7.83
(m, 2H); 13C NMR (100 MHz, CDCl3): δ 21.64, 116.32 (d, J =
21.94 Hz), 127.42, 127.73, 128.73, 130.02, 130.55, 137.67,
140.62, 144.49, 164.32 (d, J = 251.29 Hz); 19F NMR (376 MHz,
CDCl3): –111.73. HRMS-ESI(m/z): calcd for C15H14FO2S
(M+H+): 276.0699, found 276.0702.
4.3. Characterization data of products 3
4.3.1.
(E)-1-Methoxy-4-(2-tosylvinyl)benzene (3a). Yellow
1
solid, mp 100–102 °C; H NMR (400 MHz, CDCl3): δ 2.43 (s,
3H), 3.83 (s, 3H), 6.70 (d, J = 15.32 Hz, 1H), 6.88–6.91 (m, 2H),
7.33 (d, J = 8.08 Hz, 2H), 7.42 (d, J = 8.76 Hz, 2H), 7.60 (d, J =
15.32 Hz, 1H), 7.82 (d, J = 8.24 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 21.60, 55.44, 114.49, 124.80, 125.07, 127.57, 129.91,
130.32, 138.18, 141.76, 144.14, 161.98. HRMS-ESI(m/z): calcd
for C16H17O3S (M+H+): 288.0898, found 288.0896.
4.3.8.
(E)-1-Bromo-2-(2-tosylvinyl)benzene (3h). Yellow
solid, mp 88–89 °C; 1H NMR (400 MHz, CDCl3): δ 2.44 (s, 3H),
6.84 (d, J = 15.36 Hz, 1H), 7.22–7.26 (m, 1H), 7.28–7.32 (m,
1H), 7.36 (d, J = 8.00 Hz, 2H), 7.47–7.50 (m, 1H), 7.84 (d, J =
8.28 Hz, 2H), 8.03 (d, J = 15.40 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 21.65, 125.49, 127.82, 127.85, 128.17, 130.02,
130.40, 131.97, 132.47, 133.55, 137.14, 140.35, 144.62. HRMS-
ESI(m/z): calcd for C15H14BrO2S (M+H+): 336.9898, found
336.9895.
4.3.2.
(E)-1-Ethoxy-4-(2-tosylvinyl)benzene
(3b).
Light
yellow solid, mp 75–77 °C; 1H NMR (400 MHz, CDCl3): δ 1.42
(td, J = 6.98 Hz, J = 2.72 Hz, 3H), 2.43 (s, 3H), 4.03–4.09 (m,
2H), 6.69 (d, J = 15.32 Hz, 1H), 6.86–6.89 (m, 2H), 7.33 (d, J =
8.04 Hz, 2H), 7.39–7.43 (m, 2H), 7.60 (d, J = 15.36 Hz, 1H),
7.81–7.83 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 14.67,
21.60, 63.71, 114.95, 124.65, 124.89, 127.57, 129.90, 130.32,
138.24, 141.83, 144.10, 161.41. HRMS-ESI(m/z): calcd for
C17H19O3S (M+H+): 302.1055, found 302.1054.
4.3.9.
(E)-1-Bromo-3-(2-tosylvinyl)benzene (3i). Yellow
solid, mp 84–85 °C; 1H NMR (400 MHz, CDCl3): δ 2.44 (s, 3H),
6.86 (d, J = 15.40 Hz, 1H), 7.36 (d, J = 8.16 Hz, 2H), 7.38–7.41
(m, 2H), 7.52–7.54 (m, 1H), 7.58 (d, J = 15.44 Hz, 1H), 7.61–
7.62 (m, 1H), 7.82 (d, J = 8.28 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 21.66, 123.11, 127.21, 127.79, 129.11, 129.70,
130.05, 130.56, 131.04, 133.84, 134.43, 140.06, 144.68. HRMS-
ESI(m/z): calcd for C15H14BrO2S (M+H+): 336.9898, found
336.9897.
4.3.3.
(E)-1-(tert-Butoxy)-4-(2-tosylvinyl)benzene (3c). Light
1
yellow solid, mp 101–103 °C; H NMR (400 MHz, CDCl3): δ
1.37 (s, 9H), 2.43 (s, 3H), 6.73 (d, J = 15.36 Hz, 1H), 6.98 (d, J
= 8.56 Hz, 2H), 7.33 (d, J = 8.08 Hz, 2H), 7.39 (d, J = 8.60 Hz,
2H), 7.61 (d, J = 15.36 Hz, 1H), 7.82 (d, J = 8.24 Hz, 2H); 13C
NMR (100 MHz, CDCl3): δ 21.61, 28.87, 79.59, 123.67, 125.76,
127.05, 127.62, 129.59, 129.92, 138.08, 141.67, 144.20, 158.55.
4.3.10. (E)-1-Bromo-4-(2-tosylvinyl)benzene (3j). Yellow
solid, mp 80–82 °C; 1H NMR (400 MHz, CDCl3): δ 2.44 (s, 3H),
6.84 (d, J = 15.40 Hz, 1H), 7.32–7.36 (m, 4H), 7.51–7.54 (m,

2H), 7.59 (d, J = 15.44 Hz, 1H), 7.82 (d, J = 8.28 Hz, 2H); 13C
NMR (100 MHz, CDCl3): δ 21.66, 125.52, 127.76, 128.25,
129.87, 130.04, 131.32, 132.33, 137.37, 140.49, 144.61. HRMS-
ESI(m/z): calcd for C15H14BrO2S (M+H+): 336.9898, found
336.9897.
2H), 7.63 (d, J = 15.28 Hz, 1H), 7.87 (d, J = 8.24 Hz, 2H); 13C
NMR (100 MHz, CDCl3): δ 55.47, 114.58, 123.95, 124.80,
129.03, 129.60, 130.49, 139.71, 139.85, 142.87, 162.25. HRMS-
ESI(m/z): calcd for C15H14ClO3S (M+H+): 309.0352, found
309.0354.
4.3.11. (E)-1-(2-Tosylvinyl)-3,5-bis(trifluoromethyl)benzene
(3k). Light yellow solid, mp 64–66 °C; H NMR (400 MHz,
4.3.18. (E)-1-Bromo-4-((4-methoxystyryl)sulfonyl)benzene
(3r). Yellow solid, mp 114–116 °C; 1H NMR (400 MHz,
CDCl3): δ 3.84 (s, 3H), 6.68 (d, J = 15.32 Hz, 1H), 6.91 (d, J =
8.56 Hz, 2H), 7.43 (d, J = 8.60 Hz, 2H), 7.61–7.68 (m, 3H), 7.80
(d, J = 8.44 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 55.47,
114.58, 123.88, 124.78, 128.38, 129.10, 130.49, 132.58, 140.24,
142.92, 162.25. HRMS-ESI(m/z): calcd for C15H14BrO3S
(M+H+): 352.9847, found 352.9848.
1
CDCl3): δ 2.46 (s, 3H), 7.02 (d, J = 15.48 Hz, 1H), 7.38 (d, J =
8.24 Hz, 2H), 7.70 (d, J = 15.52 Hz, 1H), 7.85 (d, J = 8.28 Hz,
2H), 7.90 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 21.71, 121.42,
124.15, 128.03, 130.23, 131.23, 132.51, 134.61, 136.59, 137.99,
145.19; 19F NMR (376 MHz, CDCl3): –63.01. HRMS-ESI(m/z):
calcd for C17H13F6O2S (M+H+): 395.0540, found 395.0540.
4.3.12. (2-Tosylethene-1,1-diyl)dibenzene (3l). Light yellow
solid, mp 56–58 °C; 1H NMR (400 MHz, CDCl3): δ 2.38 (s, 3H),
6.99 (s, 1H), 7.08–7.11 (m, 2H), 7.15 (d, J = 8.04 Hz, 2H), 7.19–
7.21 (m, 2H), 7.28–7.32 (m, 4H), 7.35–7.38 (m, 2H), 7.47 (d, J =
8.28 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 21.57, 127.70,
127.81, 128.21, 128.57, 128.84, 128.94, 129.33, 129.77, 130.23,
135.57. HRMS-ESI(m/z): calcd for C21H19O2S (M+H+):
335.1106, found 335.1104.
4.3.19. (E)-1-(2-(Ethylsulfonyl)vinyl)-4-methoxybenzene (3s).
Yellow solid, mp 78–80 °C; 1H NMR (400 MHz, CDCl3): δ 1.38
(t, J = 7.46 Hz, 3H), 3.08 (q, J = 7.45 Hz, 2H), 3.85 (s, 3H), 6.66
(d, J = 15.44 Hz, 1H), 6.92–6.95 (m, 2H), 7.46–7.49 (m, 2H),
7.54 (d, J = 15.44 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 7.34,
49.57, 55.48, 114.58, 121.08, 124.87, 130.39, 144.88, 162.19.
HRMS-ESI(m/z): calcd for C11H15O3S (M+H+): 227.0742, found
227.0744.
4.3.13. 1-(tert-Butyl)-4-(1-chloro-2-tosylethyl)benzene (3m’).
Light yellow solid, mp 91–92 °C; H NMR (400 MHz, CDCl3):
4.3.20. (E)-2-((4-(tert-Butoxy)styryl)sulfonyl)thiophene
(3t).
1
1
Light yellow solid, mp 68–70 °C; H NMR (400 MHz, CDCl3):
δ 1.38 (s, 9H), 6.84 (d, J = 15.28 Hz, 1H), 6.98–7.01 (m, 2H),
7.12–7.14 (m, 1H), 7.42 (d, J = 8.60 Hz, 2H), 7.64 (d, J = 15.32
Hz, 1H), 7.67 (dd, J = 4.96 Hz, J = 1.24 Hz, 1H), 7.70 (dd, J =
3.76 Hz, J = 1.24 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
28.86, 79.67, 123.64, 125.93, 126.78, 127.96, 129.74, 133.22,
133.66, 141.94, 158.75. HRMS-ESI(m/z): calcd for C16H19O3S2
(M+H+): 323.0776, found 323.0774.
δ 1.27 (s, 9H), 2.38 (s, 3H), 3.85-3.98 (m, 2H), 5.33 (t, J = 6.96
Hz, 1H), 7.15–7.20 (m, 4H), 7.23–7.24 (m, 1H) 7.41 (s, 1H),
7.58 (d, J = 6.96 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 21.62,
31.24, 34.62, 55.10, 64.05, 125.77, 126.85, 128.16, 129.65,
135.39, 136.29, 144.61, 152.30. HRMS-ESI(m/z): calcd for
C19H24ClO2S (M+H+): 351.1186, found 351.1187.
4.3.14. (E)-1-Methoxy-4-(2-(phenylsulfonyl)vinyl)benzene
1
(3n). Light yellow solid, mp 69–71 °C; H NMR (400 MHz,
4.3.21. (E)-1-Chloro-4-(2-((4-
CDCl3): δ 3.83 (s, 3H), 6.71 (d, J = 15.36 Hz, 1H), 6.88–6.92
(m, 2H), 7.42–7.46 (m, 2H), 7.52–7.56 (m, 2H), 7.59–7.66 (m,
2H), 7.93–7.96 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 55.45,
114.53, 124.43, 124.99, 127.52, 129.28, 130.40, 133.18, 141.15,
142.32, 162.09. HRMS-ESI(m/z): calcd for C15H15O3S (M+H+):
275.0742, found 275.0745.
fluorophenyl)sulfonyl)vinyl)benzene (3u). White solid, mp 93–94
°C; H NMR (400 MHz, CDCl3): δ 6.82 (d, J = 15.36 Hz, 1H),
1
7.20–7.26 (m, 2H), 7.36–7.43 (m, 4H), 7.63 (d, J = 15.40 Hz,
1H), 7.94–7.99 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 116.74
(d, J = 22.54 Hz), 127.72, 129.47, 129.77, 130.59, 130.71,
136.56, 137.43, 141.18, 165.72 (d, J = 254.78 Hz); 19F NMR
(376 MHz, CDCl3): –103.34. HRMS-ESI(m/z): calcd for
C14H11ClFO2S (M+H+): 297.0152, found 297.0150.
4.3.15. (E)-1-((4-Methoxystyryl)sulfonyl)-2-methylbenzene
1
(3o). Light yellow solid, mp 83–85 °C; H NMR (400 MHz,
CDCl3): δ 2.63 (s, 3H), 3.84 (s, 3H), 6.70 (dd, J = 15.36 Hz, J =
3.00 Hz, 1H), 6.90–6.92 (m, 2H), 7.28–7.32 (m, 1H), 7.36–7.40
(m, 1H), 7.43–7.46 (m, 2H), 7.49 (td, J = 7.50 Hz, J = 1.30 Hz,
1H), 7.63 (d, J = 15.36 Hz, 1H), 8.11 (dd, J = 7.88 Hz, J = 1.16
Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 20.33, 55.46, 114.54,
123.81, 124.99, 126.65, 129.29, 130.35, 132.55, 133.42, 137.93,
142.66, 162.08. HRMS-ESI(m/z): calcd for C16H17O3S (M+H+):
289.0898, found 289.0897.
4.3.22. (E)-1-Bromo-3-((4-chlorostyryl)sulfonyl)benzene (3v).
Yellow solid, mp 65–67 °C; 1H NMR (400 MHz, CDCl3): δ 6.82
(d, J = 15.40 Hz, 1H), 7.37–7.39 (m, 2H), 7.42–7.46 (m, 3H),
7.65 (d, J = 15.40 Hz, 1H), 7.74–7.77 (m, 1H), 7.87–7.89 (m,
1H), 8.08 (t, J = 1.76 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
123.36, 126.26, 127.11, 129.48, 129.88, 130.60, 130.93, 136.58,
137.59, 141.99, 142.37. HRMS-ESI(m/z): calcd for
C14H11BrClO2S (M+H+): 356.9352, found 356.9351.
4.3.16. (E)-1-Methoxy-4-(2-((4-
Acknowledgments
methoxyphenyl)sulfonyl)vinyl)benzene (3p). Brown yellow solid,
1
mp 79–82 °C; H NMR (400 MHz, CDCl3): δ 3.83 (s, 3H), 3.87
We are grateful to the National Natural Science Foundation of
China (NSFC, No. 21702054) and the open project program of
Hubei Key Laboratory of Drug Synthesis and Optimization,
Jingchu University of Technology (OPP2016ZD01) for financial
support.
(s, 3H), 6.69 (d, J = 15.36 Hz, 1H), 6.88–6.91 (m, 2H), 6.98–
7.02 (m, 2H), 7.40-7.44 (m, 2H), 7.58 (d, J = 15.36 Hz, 1H),
7.84–7.88 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 55.43,
55.68, 114.48, 114.49, 125.12, 125.15, 129.74, 130.25, 132.68,
141.20, 161.91, 163.41. HRMS-ESI(m/z): calcd for C16H17O4S
(M+H+): 305.0848, found 305.0852.
Supplementary Material
4.3.17. (E)-1-Chloro-4-((4-methoxystyryl)sulfonyl)benzene
(3q). Light yellow solid, mp 112–114 °C; H NMR (400 MHz,
CDCl3): δ 3.84 (s, 3H), 6.68 (d, J = 15.32 Hz, 1H), 6.91 (d, J =
8.36 Hz, 2H), 7.44 (d, J = 8.36 Hz, 2H), 7.51 (d, J = 8.20 Hz,
Supplementary data associated with this article can be found,
in the online version, at doi:
1

6
Tetrahedron
12. P. Katrun, S. Hlekhlai, J. Meesin, M. Pohmakotr, V. Reutrakul, T.
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► A hypervalent iodine reagent-mediated sulfonylation.
► A novel and facile strategy for synthesis of vinyl sulfones.
► Metal-free, mild and neutral conditions without extra oxidants or bases.
► Good air and moisture tolerance, broad substrate scope and high chemo-selectivity.

Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: