Electrochemical Synthesis of Vinyl Sulfones by Sulfonylation of Styrenes with a Catalytic Amount of Potassium Iodide

Article abstract of DOI:10.1055/s-0040-1707249

An electrochemical sulfonylation reaction of styrenes was developed in which sodium arylsulfinates were used as sulfonylating reagents, a catalytic amount of KI was used as a redox mediator, and Bu ₄NBF ₄was used as the electrolyte. In addition to various styrenes, sodium arylsulfinates with either electron-donating or electron-withdrawing groups were tolerated.

Full text of DOI:10.1055/s-0040-1707249

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© Georg Thieme Verlag Stuttgart · New York
2020, 31, A–E
letter
A
en
P.-L. Wang et al.
Letter
Synlett
Electrochemical Synthesis of Vinyl Sulfones by Sulfonylation of
Styrenes with a Catalytic Amount of Potassium Iodide
Pei-Long Wanga,b
Hui Gao*a
Zhi-Sheng Jianga
Chao Lia
Zhi-Ao Tiana
Pin-Hua Li*a
R2
R2
O
S
+
R1
NaO2S
R1
O
KI
undivided cell
23 examples, up to 90% yield
catalytic KI and no oxidant
E-isomer only
a Key Laboratory of Green and Precise Synthetic Chemistry and
Applications Ministry of Education, Department of Chemistry,
Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China
gaohui20032@163.com
pinhuali@mail.ustc.edu.cn
b Information College, Huaibei Normal University, Huaibei, Anhui
235000, P. R. of China
Received: 21.06.2020
Accepted after revision: 19.07.2020
Published online: 26.08.2020
first involves a transition-metal catalyst and an oxidant
such as CuI/air4 or AgNO3/K2S2O85 (Scheme 1; 1B). The sec-
ond uses a reagent containing iodine (I–/oxidant system, ex-
cess I2, excess hypervalent iodine), such as NaI/CAN,6
KI/NaIO4,7 I2,8 or PhI(OAc)29 (Scheme 1; 1C).
DOI: 10.1055/s-0040-1707249; Art ID: st-2020-l0358-l
Abstract An electrochemical sulfonylation reaction of styrenes was
developed in which sodium arylsulfinates were used as sulfonylating re-
agents, a catalytic amount of KI was used as a redox mediator, and
Bu4NBF4 was used as the electrolyte. In addition to various styrenes, so-
dium arylsulfinates with either electron-donating or electron-with-
drawing groups were tolerated.
During the past decade, increasing attention has been
devoted to electrochemical synthesis, which has become a
powerful tool in organic synthesis.10 The substrate or redox
mediator can realize electron transfer directly in the elec-
trode, so electrochemical anode oxidation can take place
without hazardous or toxic oxidants. In addition, electro-
chemical synthesis usually needs a low electric current and
proceeds under mild reaction conditions. Thus, electro-
chemical synthesis is easy to perform and environmentally
friendly. In 2016, Wang and co-workers11 realized an elec-
trochemical synthesis of vinyl sulfones from cinnamic acids
through a decarboxylative cross-coupling reaction (Scheme
1; 2A). As styrenes are commercially available and the use
of styrenes directly is atom-economical, the Yuan group12
realized the electrochemical synthesis of vinyl sulfones
from styrenes directly (Scheme 1; 2B). However, there were
still some drawbacks; for example, they used eight equiva-
lents of NaI to serve simultaneously as both the redox me-
diator and the electrolyte, and the substrate scope was nar-
row, especially the scope of the sodium sulfinates. Here, we
report a convenient and efficient electrochemical synthesis
of vinyl sulfones through sulfonylation of styrenes with a
catalytic amount of KI (Scheme 1, 2C).
Key words electrochemical synthesis, vinyl sulfones, sulfonylation,
styrenes, sodium sulfinates
As an important structural motif widely present in nu-
merous pharmaceutically active agents and natural prod-
ucts, the vinyl sulfone framework has shown great applica-
tion value in pharmaceuticals.1 In addition, vinyl sulfones
are important building blocks in organic synthesis, and can
be transformed into many other useful organic com-
pounds.2 In recent years, they have attracted considerable
attention from researchers in the area of organic synthesis
and pharmaceuticals. Thus, developing a more efficient at-
om- and step-economical method for the construction of
vinyl sulfones is of great value.
Among numerous strategies for the synthesis of vinyl
sulfones, the use of alkenes as basic building blocks and in-
expensive sodium sulfinates as substrates is fascinating and
efficient. Vinyl halides, alkenylboronic acids, nitroolefins,
and cinnamic acids have been used for the synthesis of vi-
nyl sulfones (Scheme 1; 1A),3 but most of these substrates
are not commercially available, require prior functionaliza-
tion of the styrene, or are difficult to prepare. The use of
these substrates is not atom economical or environmentally
friendly. In addition, most of these reactions need transi-
tion-metal catalysts. Styrenes are commercially available,
and the use of styrenes directly is atom-economical. There
are main two strategies for using styrenes as substrates. The
We began our study by using styrene (1a) and sodium
4-methylbenzenesulfinate (2a) as model reactants in the
presence of Pt as the anode, C as the cathode, 50 mol% KI as
a redox mediator, Bu4NBF4 as an electrolyte, and AcOH as
the solvent at room temperature for 10 hours. To our de-
light, the desired vinyl sulfone product 3a was obtained, al-
beit in a relatively low 8% yield (Table 1, entry 1). Next, we
screened various solvents, including single solvents and
mixed solvents. In general, although no single solvent im-
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
P.-L. Wang et al.
Letter
Synlett
(1) Traditional methods using alkenes and sodium sulfinates as substrates
R2
R2
X
O
+
R1
R1
R1
NaO2S
(1A)
S
R1
O
X = Br, Cl, B(OH)2, NO2, COOH
R2
R2
transition-metal catalysis
oxidant
O
S
+
(1B)
NaO2S
R1
O
O
R2
R2
I– + oxidant
O
S
+
(1C)
NaO2S
or excess I2
R1
or hypervalent iodine
(2) Electrochemical methods using alkenes and sodium sulfinates as substrates
R2
Previous work:
R2
O
O
COOH
S
O
R1
NaO2S
+
(2A)
(2B)
electrode
R1
R2
R2
NaI (8 equiv.)
electrode
+
R1
NaO2S
S
R1
O
This work:
R2
R2
KI (0.5 equiv.)
O
+
R1
NaO2S
(2C)
S
electrode
without any oxidant
R1
O
catalytic KI and no oxidant
wider substrate scope
E-isomer only
Scheme 1 Methods for the construction of vinyl sulfones using alkenes and sodium arylsulfinates as substrates
proved the yield further (entries 2 and 3), the use of mixed
solvents dramatically improved the yield. Of the mixed sol-
vents, 1:1 v/v DMF–AcOH was used first (entry 4), and to
our excitement resulted in a yield of 37%. When DMSO–
AcOH was used, a higher yield (71%) was achieved (entry 5).
We then tested NMP, MeCN, MeOH, 1,4-dioxane, pyridine,
and acetone, which are commonly used in electrochemical
syntheses, as cosolvents with AcOH (entries 6–11). To our
disappointment, none of these resulted in any obvious im-
provement. After screening the volume ratio of DMSO and
AcOH, we found that the best ratio was 1:1; other ratios
(2:1, 1:2, 5:1, or 1:5) had negative effects on the yield (en-
tries 12–15). The yield was reduced when the amount of KI
was decreased (entries 16 and 17). The effect of supporting
electrolytes was also examined. The supporting electrolytes
did not have a marked effect on the electrosynthesis. Bu4-
NOAc gave a 66% yield, which was slightly lower than that
achieved by using Bu4NBF4 (entry 18). Bu4NPF6 and Bu4NC-
lO4 gave lower yields (entries 19 and 20). Increasing the
temperature from room temperature to 50 °C had a slight
positive effect on the yield, increasing it to 73% (entry 21).
Finally, we used N2 as a protective gas instead of an air at-
mosphere and, to our delight, the yield improved to 81%
(entry 22). Therefore, a Pt anode, a C cathode, a 12 mA con-
stant current, 50 mol% KI, and one equivalent of Bu4NBF4 at
50 °C in 1:1 DMSO–AcOH were chosen as the optimal con-
ditions for this electrochemical sulfonylation reaction of
styrenes.
With our optimized reaction conditions in hand,13 we
further explored the scope of this reaction (Scheme 2).14
We first tested the scope of the styrene. Substituent effects
on the phenyl ring were investigated, and the results re-
vealed that both electron-donating and electron-withdraw-
ing groups were well tolerated in our system, affording the
corresponding vinyl sulfones 3b–j in moderate to excellent
yields. An alkyl-group-substituted styrene was suitable for
this arylation reaction (3b). Moreover, a diversity of halo-
gen substituents, including F, Cl, and Br, on the phenyl rings
were also compatible with the current method (3c–e, 3i,
and 3j). Chloro and bromo functionalities are useful in tran-
sition-metal-catalyzed coupling reactions, and they can
also be transformed into many other functionalities. Nota-
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

C
P.-L. Wang et al.
Letter
Synlett
R2
Pt(+) l C(–), I = 12 mA
KI (50 mol%)
O
S
R1
+
SO2Na
R1
O
Bu4NBF4 (1 equiv)
DMSO/AcOH (1:1 v/v)
50 °C, 10 h, N2
R2
1
2
3
O
S
O
O
S
O
S
O
S
O
S
O
O
O
O
F
Cl
Br
3a, 81%
3b, 82%
3c, 73%
3d, 82%
3e, 77%
O
S
O
O
S
O
S
O
S
O
S
O
O
O
O
O
F3C
O
NC
F
Br
3f, 69%
3g, 69%
3h, 83%
3i, 86%
3j, 89%
F
Cl
O
S
O
O
S
O
O
S
O
O
S
O
S
O
O
3k, 80%
3l, 62%
3m, 87%
3n, 90%
3o, 73%
Br
O
CF3
CN
O
S
O
S
O
S
O
S
O
S
O
O
O
O
O
3p, 87%
3q, 88%
3r, 90%
3s, 52%
3t, 88%
O
S
O
S
O
S
Cl
O
O
O
Cl
3u, 88%
3v, 89%
3w, 73%
Scheme 2 Electrochemical sulfonylation substrate scope
bly, meta-substituted styrenes exhibited better reactivity
than did para-substituted styrenes. In addition to styrenes,
2-vinylnaphthalene also exhibited a good reactivity (3k).
Next, we examined the substrate scope of the sodium sulfi-
nate 2. Unsubstituted sodium benzenesulfinate reacted
well, giving 3l in a moderate yield. Sodium benzenesulfi-
nates bearing electron-donating or electron-withdrawing
groups also reacted well (3m–v). Halogen substituents (3n–
p) were well tolerated in our system. We tested the influ-
ence of position of the substituent. In addition to para-sub-
stituted substrates, both meta- and ortho-substituted sub-
strates were suitable for this sulfonylation reaction (3t–v).
Like meta-substituted styrenes, a meta-substituted sodium
benzenesulfinate exhibited a better reactivity than did a
para-substituted analogue (3t and 3u). The reactivity of an
ortho-substituted sodium benzenesulfinate was slightly
better than that of a meta-substituted sodium benzenesul-
finate (3v). Finally, -methylstyrene was used as the sub-
strate, but none of the desired vinyl sulfone product was
formed; instead, the allylic sulfonation product 3w was ob-
tained.
Based on previous reports, a plausible mechanism for
the electrochemical sulfonylation reaction is proposed, as
shown in Scheme 3. First, iodide is transformed into molec-
ular iodine by anodic oxidation; this then reacts with the
sodium arylsulfinate to generate an unstable sulfonyl
O
S
O
S
R1-SO2Na
Anode
Cathode
1/2 I2
R1
R1
2 H+
I
O
A
O
B
R2
I
I
O
S
O
S
R1
R1
H2
I–
HI
R2
R1
R2
O
O
D
C
O
S
R2
O
E
Scheme 3 Plausible reaction mechanism
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E

D
P.-L. Wang et al.
Letter
Synlett
Table 1 Optimization of the Reaction Conditionsa,b
were compatible with this reaction. Notably, when -meth-
ylstyrene was used as the substrate, an allylic sulfonation
product was formed instead of a vinyl sulfone.
Pt(+) l C(–), I = 12 mA
KI (50 mol%)
O
S
+
SO2Na
O
electrolyte (1 equiv)
solvent, rt, 10 h, air
Funding Information
1a
2a
3a
We gratefully thank the Anhui Provincial Natural Science Foundation
(No. 1808085QB29) and Key Project of Provincial Natural Science Re-
search Foundation of Anhui Universities, China (No. KJ2018A0675,
Entry
Electrolyte
Solvent
Yield (%)
1
2
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NBF4
Bu4NOAc
Bu4NPF6
Bu4NClO4
Bu4NBF4
Bu4NBF4
AcOH
8
KJ2018A0389) for financial support.
N
aturalS
c
i
e
n
c
e
F
o
u
n
d
ati
o
n
of
A
n
h
u
iPro
v
i
n
c
e
(1
8
0
8
0
8
5
Q
B
2
9)
MeOH
trace
0
3
EtOH
Supporting Information
4
DMF–AcOH (1:1)
DMSO–AcOH (1:1)
NMP–AcOH (1:1)
MeCN–AcOH (1:1)
MeOH–AcOH (1:1)
1,4-dioxane–AcOH (1:1)
pyridine–AcOH (1:1)
acetone–AcOH (1:1)
DMSO–AcOH (2:1)
DMSO–AcOH (1:2)
DMSO–AcOH (5:1)
DMSO–AcOH (1:5)
DMSO–AcOH (1:1)
DMSO–AcOH (1:1)
DMSO–AcOH (1:1)
DMSO–AcOH (1:1)
DMSO–AcOH (1:1)
DMSO–AcOH (1:1)
DMSO–AcOH (1:1)
37
71
49
19
20
0
5
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1707249.
S
u
p
p
orit
n
gInformati
o
n
S
u
p
p
orit
n
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o
n
6
7
8
References and Notes
9
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21e
22e,f
49
trace
65
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trace
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81
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a Reaction conditions: Pt anode, C cathode, I = 12 mA, undivided cell, 1a (1
mmol), 2a (2 mmol), KI (50 mol%), electrolyte (1 mmol, 1 equiv), solvent (6
mL), rt, 10 h, air.
b Isolated yield.
c 30 mol% KI was used.
d 10 mol% KI was used.
e At 50 °C
f N2 instead of air.
iodide intermediate A. Subsequent decomposition results in
the formation of a sulfonyl radical and an iodine radical.
Next, the sulfonyl radical and iodine radical add sequential-
ly to the olefin to give intermediate D. Finally, HI elimina-
tion from D gives the desired sulfonation product E and io-
dide, which is re-oxidized at the anode to regenerate mo-
lecular iodine.
In summary, we have developed an electrochemical sul-
fonylation of styrenes by employing sodium arylsulfinates
as sulfonylation reagents. A catalytic amount of KI as a re-
dox mediator was sufficient for this reaction. The scope of
the substrate was wide. A variety of functional groups, not
only on the styrene, but also on the sodium arylsulfinate,
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Letter
Synlett
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mL) were added sequentially from a syringe. Electrolysis was
carried out at a constant current of 12 mA at 50 °C for 10 h. The
mixture was then cooled to rt and filtered through a plug of
silica, eluting with EtOAc. The filtrate was washed with H2O
(×3) and extracted with EtOAc. The organic layer was washed
with brine, dried (Na2SO4), and evaporated to dryness under
reduced pressure. The residue was purified by column chroma-
tography [silica gel, PE–EtOAc (5:1)].
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White solid; yield: 209.4 mg (81%); mp 119–120 °C. 1H NMR
(600 MHz, CDCl3):  = 7.83 (d, J = 8.3 Hz, 2 H), 7.66 (d, J = 15.4
Hz, 1 H), 7.48–7.47 (m, 2 H), 7.42–7.34 (m, 5 H), 6.85 (d, J = 15.4
Hz, 1 H), 2.43 (s, 3 H). 13C NMR (151 MHz, CDCl3):  = 144.5,
142.1, 137.8, 132.6, 131.2, 130.1, 129.2, 128.7, 127.8, 127.7,
21.8. HRMS (ESI): m/z [M + H]+ calcd for C15H15O2S: 259.0787;
found: 259.0789.
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4876.
(E)-4-(2-Tosylvinyl)benzonitrile (3h)
White solid; yield: 234.6 mg (83%); mp 125–127 °C. 1H NMR
(600 MHz, CDCl3):  = 7.83 (d, J = 8.3 Hz, 2 H), 7.69 (d, J = 8.3 Hz,
2 H), 7.65 (d, J = 15.5 Hz, 1 H), 7.58 (d, J = 8.3 Hz, 2 H), 7.37 (d, J =
8.0 Hz, 2 H), 6.96 (dd, J = 15.4, 0.8 Hz, 1 H), 2.45 (s, 3 H). 13C NMR
(151 MHz, CDCl3):  = 145.1, 139.4, 136.9, 136.8, 132.9, 131.4,
130.3, 129.0, 128.1, 118.2, 114.3, 21.8. HRMS (ESI): m/z [M + H]+
calcd for C16H14NO2S: 284.0740; found: 284.0738.
(E)-2-(2-Naphthyl)vinyl 4-Tolyl Sulfone (3k)
Yellow solid; yield: 246.9 mg (80%); mp 160–162 °C. 1H NMR
(400 MHz, CDCl3):  = 7.91–7.79 (m, 7 H), 7.54–7.49 (m, 3 H),
7.34 (d, J = 7.9 Hz, 2 H), 6.96 (d, J = 15.4 Hz, 1 H), 2.42 (s, 3 H). 13
C
NMR (101 MHz, CDCl3):  = 144.5, 142.1, 137.9, 134.5, 133.2,
131.0, 130.1, 130.0, 129.0, 128.8, 127.9, 127.8, 127.7, 127.1,
123.5, 21.7. HRMS (ESI): m/z [M + H]+ calcd for C19H17O2S:
309.0944; found: 309.0948.
2-Chlorophenyl (E)-2-Phenylvinyl Sulfone (3v)
White solid; yield: 247.8 mg (89%); mp 93–94 °C. 1H NMR (400
MHz, CDCl3):  = 8.22 (d, J = 7.7 Hz, 1 H), 7.77 (d, J = 15.4 Hz, 1
H), 7.57–7.39 (m, 8 H), 7.08 (d, J = 15.4 Hz, 1 H). 13C NMR (101
MHz, CDCl3):  = 145.4, 138.2, 134.6, 132.9, 132.4, 132.0, 131.5,
130.8, 129.2, 128.8, 127.6, 125.3. HRMS (ESI): m/z [M + H]+ calcd
for C14H15ClNO2S: 296.0507; found: 296.0513
(12) Luo, Y.-C.; Pan, X.-J.; Yuan, G.-Q. Tetrahedron 2015, 71, 2119.
(13) Electrochemical Sulfonylation of Styrenes 3a–w; General
Procedure
2-Phenylprop-2-en-1-yl 4-Tolyl Sulfone (3w)
White solid; yield: 197.9 mg (73%); mp 97–98 °C. 1H NMR (400
MHz, CDCl3):  = 7.67–7.64 (m, 2 H), 7.29–7.21 (m, 7 H), 5.59 (s,
1 H), 5.21 (s, 1 H), 4.25 (s, 2 H), 2.39 (s, 3 H). 13C NMR (151 MHz,
CDCl3):  = 144.7, 139.0, 136.7, 135.5, 129.6, 128.8, 128.5, 128.0,
126.3, 121.9, 62.2, 21.7. HRMS (ESI): m/z [M + H]+ calcd for
An undivided cell equipped with a Pt anode (1.0 × 1.0 × 0.02
cm) and a graphite rod cathode was charged with the appropri-
ate sodium arylsulfinate (2 mmol), KI (0.5 mmol), and Bu4NBF4
(1 mmol). The vessel was evacuated and backfilled with N2 (×3).
The appropriate styrene (1 mmol), DMSO (3 mL), and AcOH (3
C
16H16NaO2S: 295.0763; found: 295.0765.
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–E