Electrosynthesis of vinyl sulfones from alkenes and sulfonyl hydrazides mediated by KI: Аn electrochemical mechanistic study

Article abstract of DOI:10.1016/j.tet.2017.10.047

A variety of vinyl sulfones were prepared from alkenes and sulfonyl hydrazides via electrochemical oxidative sulfonylation. The reaction proceeds in an experimentally convenient undivided electrochemical cell equipped with graphite and iron electrodes employing KI as a redox catalyst and a supporting electrolyte. Applying extremely high current density up to 270 mA/cm² permits rapid synthesis in a compact reactor and with small surface area electrodes. A possible reaction mechanism was proposed with the use of cyclic voltammetry. It is the combination of anodic and cathodic processes in this reaction that makes it possible to obtain products under mild conditions with yields from moderate to high.

Full text of DOI:10.1016/j.tet.2017.10.047

Accepted Manuscript
Electrosynthesis of vinyl sulfones from alkenes and sulfonyl hydrazides mediated by
KI: Аn electrochemical mechanistic study
Alexander O. Terent'ev, Olga M. Mulina, Dmitry A. Pirgach, Alexey I. Ilovaisky,
Mikhail A. Syroeshkin, Nadezhda I. Kapustina, Gennady I. Nikishin
PII:
S0040-4020(17)31084-0
10.1016/j.tet.2017.10.047
TET 29050
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 10 June 2017
Revised Date: 3 October 2017
Accepted Date: 17 October 2017
Please cite this article as: Terent'ev AO, Mulina OM, Pirgach DA, Ilovaisky AI, Syroeshkin MA,
Kapustina NI, Nikishin GI, Electrosynthesis of vinyl sulfones from alkenes and sulfonyl hydrazides
mediated by KI: Аn electrochemical mechanistic study, Tetrahedron (2017), doi: 10.1016/
j.tet.2017.10.047.
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Electrosynthesis of vinyl sulfones from
alkenes and sulfonyl hydrazides mediated by
KI: аn electrochemical mechanistic study
Leave this area blank for abstract info.
Alexander O. Terent’eva,b, , Olga M. Mulinaa, Dmitry A. Pirgacha,b, Alexey I. Ilovaiskya, Mikhail A.
Syroeshkina, Nadezhda I. Kapustinaa, and Gennady I. Nikishina
a N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, 119991, Russian Federation
b D.I. Mendeleev University of Chemical Technology of Russia, Moscow, 125047, Russian Federation

1
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Tetrahedron
journal homepage: www.elsevier.com
Electrosynthesis of vinyl sulfones from alkenes and sulfonyl hydrazides mediated by
KI: аn electrochemical mechanistic study
Alexander O. Terent’eva,b, , Olga M. Mulinaa, Dmitry A. Pirgacha,b, Alexey I. Ilovaiskya, Mikhail A.
Syroeshkina, Nadezhda I. Kapustinaa and Gennady I. Nikishina
a N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991, Russian Federation
b D.I. Mendeleev University of Chemical Technology of Russia, Moscow, 125047, Russian Federation
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A variety of vinyl sulfones were prepared from alkenes and sulfonyl hydrazides via
electrochemical oxidative sulfonylation. The reaction proceeds in an experimentally convenient
undivided electrochemical cell equipped with graphite and iron electrodes employing KI as a
redox catalyst and a supporting electrolyte. Applying extremely high current density up to 270
mA/cm2 permits rapid synthesis in a compact reactor and with small surface area electrodes. A
possible reaction mechanism was proposed with the use of cyclic voltammetry. It is the
combination of anodic and cathodic processes in this reaction that makes it possible to obtain
products under mild conditions with yields from moderate to high.
Available online
Keywords:
vinyl sulfones
sulfonyl hydrazides
alkenes
2009 Elsevier Ltd. All rights reserved
.
electrosynthesis
oxidation
1. Introduction
of electrochemical methodologies through oxidative C-S
coupling, benzothiazoles,37 oxindoles,38 thiocyanato-derivatives
of α,β-unsaturated carbonyl compounds,39 β-ketosulfones,40
thioaryl aromatic compounds41 and sulfonyl indoles42 were
synthesized. As for vinyl sulfones, they have been synthesized
from sodium sulfinates as S-reagents and styrenes43 or cinnamic
acids44 as C-reagents utilizing electric current.
Vinyl sulfones attract considerable interest in the area of
medicinal and organic chemistry. The vinyl sulfone moiety is a
key structural unit in antibacterial,1 antiprotozoal,2 anti HIV3 and
neuroprotective agents.4 They are widely applied as reagents in
Michael addition chemistry5,6 and the syntheses of natural
compounds.7,8 Traditionally vinyl sulfones are prepared through
the oxidation of vinyl sulfides,9 Horner–Wadsworth–Emmons
reactions between sulfonyl phosphonates and carbonyl
compounds,10 Knoevenagel condensations of sulfonylacetic acids
with aromatic aldehydes11 and β-elimination of halosulfones12 or
selenosulfones13. Taking the importance of vinyl sulfones into
consideration,14 the development of simple and efficient methods
for their preparation is still desirable. In this connection, in the
last few years, the direct coupling of the sulfonyl derivatives with
an alkene15-18 or alkyne moiety19-21 has been paid careful
attention as an efficient strategy for the construction of vinyl
sulfones.
Performing the electrochemical processes under high current
densities (> 100 mA/cm2) is widely used in inorganic chemistry
(e.g., Cl2/NaOH production, extraction of Al and Cu). As for
organic electrochemical reactions, conducting these processes
under high current densities often leads to an increasing number
of side processes. That is why organic electrosynthetic reactions
are usually carried out under current densities, not surpassing 50
mA/cm2.45-49
In this context, we report an electrochemical reaction between
alkenes and sulfonyl hydrazides using a graphite anode and iron
cathode, proceeding under a high current density of 60-270
mA/cm2, leading to vinyl sulfones in yields from moderate to
high. This transformation is tolerant to both electron-
withdrawing and electron-donating substituents in the starting
reagents and owing to usage of ultra high current densities runs
fast in comparison with previous electrochemical approaches,
which permits the use of our methodology as a preparative route
to vinyl sulfones.
Oxidative strategies are finding ever-widening application in
the construction of C-S bonds. Among oxidants used for this
purpose, such as transition-metal salts and complexes,22,23
NBS,24,25
K2S2O8,26
peroxides,27
I2/TBHP28,29
and
TBAI/TBHP30,31 systems, electric current is one of the most
environment-friendly and easiest in handle. This is the reason
why redox processes with organic compounds are realized using
electrochemical techniques now.32-36 For example, with the use
———
Corresponding author. Tel.: +7-916-385-4080; fax: +7-499-135-5328; e-mail: terentev@ioc.ac.ru

2
Tetrahedron
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2. Results and discussion
The influence of supporting electrolyte and its amount, molar
ratio of starting reagents, solvent type, the amount of passed
electric current and its density, and electrode materials on 3aa
yield was explored. The reaction between 1a and 2a in 1:1 molar
ratio, with the usage of KI as an electrolyte, CH3CN-H2O as a
solvent and 7 F/mol of electric current afforded desired 3aa in
59% yield (entry 1).
Electrosynthesis of vinyl sulfones 3aa-3fa, 3ab-3ap from
sulfonyl hydrazides 1a-1f and alkenes 2a-2p was conducted in
СH3CN–H2O or THF–H2O solution with KI, NH4I, KBr, and
NH4Br as supporting electrolytes in an undivided cell under
constant current conditions (Scheme 1).
Scheme 1. Electrosynthesis of vinyl sulfones 3aa-3fa and 3ab-3ap from sulfonyl hydrazides 1a-1f and alkenes 2a-2p (in the
codification of 3 the first letter index refers to the hydrazide 1 moiety, the second letter index to the alkene 2 moiety).
Table 1. Optimization of the reaction conditions for the synthesis of vinyl sulfone 3aa from
and styrene 2aa
p-toluenesulfonyl hydrazide 1a
.
Molar ratio
Supporting electrolyte molar
N,
Current density,
Anode-
Yield
3aa, % b
59
Entry
Solvent
1a : 2a
1:1
ratio (mol / mol 1a)
F/mol 1a
mA/cm2
60
Cathode
C – Fe
1
2
KI (3)
CH3CN-H2O
CH3CN-H2O
CH3CN-H2O
CH3CN-H2O
CH3CN-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
THF-H2O
7
1:2
1:3
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
KI (3)
KI (3)
7
7
60
60
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
C – Fe
Pt – Fe
Pt – Pt
66
67
51
56
93
93
82
60
91
37
0
3
4
KI (3)
4
60
5
KI (3)
10
7
60
6
KI (3)
60
7
KI (2)
7
60
8
KI (1)
7
60
9
KI (0.5)
NH4I (2)
KBr (2)
NH4Br (2)
KI (2)
7
60
10
11
12
13
14
15
16
7
60
7
60
7
60
7
150
270
270
270
90
90
84
90
KI (2)
7
KI (2)
7
KI (2)
7
a
General procedure: the solution of p-toluenesulfonyl hydrazide 1a (300 mg, 1.61 mmol), styrene 2a (1.61-4.83 mmol, molar ratio 1-3 mol 2a/mol 1a) and
supporting electrolyte (1.61-4.83 mmol, molar ratio 1-3 mol/mol 1a) in 30 mL of CH3CN-H2O (1:1) or THF-H2O (1:1) was electrolyzed under constant current
conditions (60, 150 or 270 mA/cm2 at 30 °C) under magnetic stirring.
b Isolated yield.
The search of optimal reaction conditions for vinyl sulfone
electrosynthesis was carried out using p-toluenesulfonyl
hydrazide 1a and styrene 2a as model substrates (Table 1).
Firstly, the most preferable ratio of starting reagents was
found: it was shown that two-fold excess of styrene 2a per
hydrazide 1a is optimal (entries 2-3). Decreasing (entry 4) or
increasing (entry 5) the electric current passed through the

3
reaction didn’t give better results. The solvent turned out to have
a great influence on the yield of target vinyl sulfone 3aa. The
replacement of CH3CN-H2O for THF-H2O improved the 3aa
yield up to 93% (entry 6). The effect of the amount of supporting
electrolyte (KI) was also investigated. When 2 mol of KI per mol
hydrazide 1a was employed (entry 7) the yield of target vinyl
sulfone remained the same. The yield of 3aa decreased when 1 or
0.5 mol KI per mol hydrazide 1a was used (entries 8-9). The
nature of supporting electrolyte was demonstrated to play a
crucial role in the efficiency of vinyl sulfone electrosynthesis.
Among supporting electrolytes NH4Br, KBr, NH4I, and KI, the
latter proved to be a superior one in THF-H2O solution (entries
10-12). As shown in entries 13-14, electrochemical synthesis of
vinyl sulfone 3aa from sulfonyl hydrazide 1a and styrene 2a can
be successfully conducted with extremely high current density.
electrolyte, graphite plate as the anode and Fe plate as the
ACCEPTED MANUSCRIPT
cathode; the reaction proceeds best in THF-H2O as a solvent
(entry 7). Under optimized reaction conditions the scope of this
electrochemical methodology for the preparation of vinyl
sulfones was tested. Our attention was extended to different
sulfonyl hydrazides 1 and alkenes 2 (Table 2).
Sulfonyl hydrazides bearing both electron-donating and
electron-withdrawing groups afforded target vinyl sulfones in
high yields except for the case of p-nitrobenzenesulfonyl
hydrazide 1f, which could be due to the reduction of the nitro
group on the cathode. When styrenes with various substituents in
the ortho-, meta- and para-positions were employed, the desired
vinyl sulfones were isolated with yields from moderate to high.
Table 2. Structures and yields of vinyl sulfones 3 prepared from sulfonyl hydrazides 1a-1f and alkenes 2a-2p a,b
.
3aa, 93% (90%)
3ba, 89% (78%)
3fa, 18% (49%)
3ca, 85% (34%)
3ab, 85% (93%)
3da, 79% (66%)
3ea, 74% (77%), 68% c
3ac, 92% (61%)
O
S
O
Cl
3ad, 78% (71%)
3ah, 61% (65%)
3ae, 95% (87%)
3ai, 90% (87%)
3af, 79% (63%), 70% c
3aj, 50% (43%) d
3ag, 93% (87%)
3ak, 55% (70%), 50% c
3al, 73% (30%)
3am, 53% (32%)
3an, 44% (77%), 35% c
3ao, 32% (5%) e
3ap, 25% (5%)
a General procedure: the solution of sulfonyl hydrazide 1a-1f (300 mg, 1.01-1.61 mmol), alkene 2a-2p (1.93-3.22 mmol, molar ratio 1.2 or 2 mol 2/mol 1) and
supporting electrolyte KI (2.02-3.22 mmol, molar ratio 2 mol/mol 1) in 30 mL of THF-H2O (1:1) was electrolyzed under constant current conditions (current
density 60 mA/cm2 or 270 mA/cm2 at 30 °C) under magnetic stirring.
b Isolated yields. First yield, current density 60 mA/cm2. Second yield, in parentheses, current density 270 mA/cm2.
c Isolated yield when molar ratio 1.2 mol 2/mol 1 was used at current density 60 mA/cm2.
d 1-(4-Methoxyphenyl)-2-tosylethanol (4aj) was isolated as the byproduct in 41% (33%) yield.
e 1-[(4-Methylphenyl)sulfonyl]-2-phenylpropan-2-ol (4ao) was isolated as the byproduct in 37% (30%) yield.
It makes possible to carry out this process rapidly using small
surface area electrodes. Further screening of electrode materials
indicated that graphite or Pt anodes and Fe or Pt cathodes gave
comparable yields of 3aa (entries 15-16). The application of high
current densities (entries 13-16) permitted about 0.4 g (1.6 mmol)
of target vinyl sulfones to be prepared in 12 minutes. Fro
m the results described above, we concluded that the
optimal reaction conditions are defined as applying of two-fold
excess of styrene 2a over hydrazide 1a, 2 mol of KI per mol 1a
as the supporting
Decreasing the amount of styrene to 1.2 equiv. led to a slight
decrease in the yield of products 3ea, 3af, 3ak, 3an. Applying p-
methoxystyrene 2j and α-methylstyrene 2o in this reaction
resulted in the formation of the corresponding β-hydroxysulfones
4aj and 4ao as side products. This observation is useful for
understanding the reaction pathway (vide infra). Applying this
methodology, sulfonyl hydrazides can be also coupled with
aliphatic alkenes, such as 1-octene, providing target vinyl sulfone
3ap in 25% yield. All vinyl sulfones were also synthesized with
current density 270 mA/cm2. As shown in Table 2, the yield of
the majority of products does not dramatically change under
these conditions. To demonstrate the possibility of using this

4
Tetrahedron
ACCEPTED MANUSCRIPT
method as a preparative one, a multigram scale experiment was
which further oxidizes p-toluenesulfonyl hydrazide 1a resulting
conducted (Scheme 2). When 16 mmol of hydrazide 1a was
reacted with 32 mmol of styrene 2a under the optimized
conditions (Table 1, entry 7), product 3aa was isolated in 93%
yield.
in the generation of p-toluenesulfonyl iodide A.43 In the
processes of iodide-anion oxidation and formation of p-
toluenesulfonyl iodide A, hypoiodites, iodates or periodates can
be also involved.55-57 They are mainly produced as a result of the
reaction between molecular iodine and hydroxide-anions forming
by the cathodic reduction of H2O.58-61 The resulting p-
toluenesulfonyl iodide A is reduced on the cathode and gives
anion B. This was confirmed by investigation of the
electrochemical behaviour of freshly prepared p-toluenesulfonyl
iodide A in CH3CN (Fig. 2).
Figure 2. CV curve for a 5.0 mmol/L solution of p-
Scheme 2. Scaling up of the synthesis of vinyl sulfone 3aa
from sulfonyl hydrazide 1a and styrene 2a
.
To study plausible reaction mechanism some additional
experiments with the use of cyclic voltammetry (CV) on a
working glassy-carbon electrode were carried out. CH3CN or
CH3CN–H2O (1:1) was used as a solvent. Tetrabutylammonium
perchlorate, which cannot be oxidized in such experimental
conditions, was chosen as a supporting electrolyte. Firstly,
investigation of the redox properties of p-toluenesulfonyl
hydrazide 1a, styrene 2a and KI in CH3CN–H2O (1:1) solution
was conducted. The obtained CV curves are shown in Fig. 1.
Styrene 2a is oxidized most difficultly; the corresponding peak
(+ 1.72 V) overlaps with discharge of the background (oxidation
of water, ~ +2.0 V vs SCE). The chemically irreversible peak at
+ 1.36 V is responsible for the oxidation of p-toluenesulfonyl
hydrazide 1a. Iodide-anion oxidation runs in the earliest
potentials at +0.53 V. Therefore, we can conclude that under
experimental conditions KI acts both as a supporting electrolyte
and as a redox catalyst and iodide-anion oxidation takes place.
The products of iodide-anion oxidation can participate further in
the oxidative coupling of p-toluenesulfonyl hydrazide 1a and
styrene 2a.
toluenesulfonyl iodide in 0.1 M Bu4NClO4 in CH3CN on a
working glassy-carbon electrode (d = 1.7 mm) under a scan
rate of 0.1 V/s.
The absence of peak on the reverse part of curve and
significant increasing of the forward peak current (Fig. 2)
comparing with 1e level (ferrocene related, Fig. 3) demonstrates
that the reduction of A runs through ECE (electron transfer-
chemical reaction-electron transfer) mechanism62-64 in rather
early potential range (-0.75 V vs SCE). Previously65 electrolysis
of p-toluenesulfonyl chloride under similar conditions also
resulted in the formation of p-toluenesulfonyl anion as the main
product. After that, anion B is oxidized to the radical C, it is
supported by voltammetry study of sodium p-toluenesulfinate in
CH3CN–H2O (1:1). The chemically irreversible peak at +0.78 V
vs SCE is responsible for the oxidation of p-toluenesulfinate
anion B (Fig. 3). The peak current at this CV curve is the same as
the peak current at ferrocene CV curve under equal scan rate and
concentration. Hence, we can conclude that single electron
oxidation takes place. In addition, it is possible that S-centered
radical C is directly formed from p-toluenesulfonyl iodide A.42 In
the next step C is trapped with styrene 2a.66-70 As a result, C-
centered benzyl radical D is formed, which is oxidized on the
anode, leading to benzyl cation E.71,72 To form the desired vinyl
sulfone 3aa cation E liberates H+ or reacts with iodide anion,
73
resulting in the generation of iodosulfone F, which can lead to
3aa formation through HI elimination.15,16,30,66 If benzyl cation E
is stable enough, it can be hydroxylated, providing β-
hydroxysulfones 4. They were isolated when p-methoxystyrene
2j and α-methylstyrene 2o were used as starting reagents
(Scheme 4). The impossibility of vinyl sulfone 3 formation
through dehydroxylation was confirmed by a control experiment
(see Experimental), where β-hydroxysulfone 4ao was
electrolyzed under the experimental conditions. As a result, its
conversion into vinyl sulfone 3ao was not observed.
Figure 1. CV curves for a 3.0 mmol/L solution of p-
toluenesulfonyl hydrazide 1a (blue), 5.0 mmol/L solutions of
styrene 2a (red) and KI (green) in 0.1 M Bu4NClO4 in
CH3CN–H2O (1:1) on a working glassy-carbon electrode (d =
1.7 mm) under a scan rate of 0.1 V/s.
As for the mechanism of electrochemical formation of
vinyl sulfones
3 from hydrazides 1 and alkenes 2, we
propose (Scheme 3) that on the first reaction step iodide-
,50-54
anion is oxidized on the anode to molecular iodine,40

5
ACCEPTED MANUSCRIPT
2 I
H2O
I2
OH
H2 + OH
O
S
I
NHNH2
O
1a
I
I
2
,
O
S
I
O
A
O
Figure 3. CV curves for 3.0 mmol/L solutions of sodium p-
toluenesulfinate (blue) and ferrocene (red) in 0.1
M
S
Bu4NClO4 in CH3CN–H2O (1:1) on a working glassy-carbon
electrode (d = 1.7 mm) under a scan rate of 0.05 V/s.
O
B
A
3. Conclusions
O
S
In summary, we have demonstrated an effective
electrochemical strategy for the preparation of vinyl sulfones
from alkenes and sulfonyl hydrazides in yields from moderate to
high. The reaction proceeds in an undivided electrochemical cell
equipped with available graphite anode and iron cathode,
employing KI as both a redox catalyst and a supporting
electrolyte. A wide range of substrates with various substituents
proved to be compatible with the process. A scale up experiment
evidenced the possibility of using this methodology as a
preparative route to vinyl sulfones. A possible reaction pathway
was also proposed on the basis of electrochemical experiments.
- I
O
C
2a
O
S
O
D
4. Experimental
O
S
NMR spectra were recorded on Bruker Avance II 300 MHz
instrument. Chemical shifts were measured relative to residual
solvent peaks set to δ 7.25 and δ 77.0 (CDCl3), δ 2.50 and δ
39.51 (DMSO-d6). High resolution mass spectra (HRMS) were
measured on a Bruker maXis instrument equipped with an
electrospray ionization (ESI) ion source74. The measurements
were done in a positive ion mode (interface capillary voltage
4500 V); the mass ratio was from m/z 50 to 3000 Da;
external/internal calibration was done with Electrospray
Calibrant Solution. A syringe injection was used for solutions in
CH3CN (flow rate 3 ꢀL/min). Nitrogen was applied as a dry gas;
the interface temperature was set at 180 °C. The TLC analyses
were carried out on pre-coated TLC sheets ALUGRAM Xtra SIL
G/UV254. The melting points were determined on a Kofler hot-
stage apparatus. Chromatography was performed on silica gel
(60-200 mesh).
O
E
I
I
O
S
O
- H
F
- HI
O
S
O
3aa
Scheme 3. Proposed mechanism of the reaction of p-
toluenesulfonyl hydrazide 1a with styrene 2a.
p-Toluenesulfonohydrazide (1a), vinylbenzene (2a), 1-
methyl-4-vinylbenzene (2b), 1-methyl-3-vinylbenzene (2c), 1-
methyl-2-vinylbenzene (2d), 1-tert-butyl-4-vinylbenzene (2f), 1-
chloro-4-vinylbenzene (1g), 1-fluoro-4-vinylbenzene (2h), 1-
bromo-3-vinylbenzene (2i), 1-methoxy-4-vinylbenzene (2j),
1,2,3,4,5-fluoro-6-vinylbenzene (2n), isopropenylbenzene (2o),
octene-1 (2p), 4-methoxybenzenesulfonyl chloride, 4-
iodobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride,
OH
O
S
R''
O
S
R''
H2O
O
O
R'
R'
4aj, 4ao
3aj', 3ao'
3aj': R' = OMe, R'' = H
3ao': R' = H, R'' = Me
4-chlorobenzenesulfonyl
chloride, 4-iso-propylbenzaldehyde, 3-methoxybenzaldehyde, 2-
methoxybenzaldehyde, 4-nitrobenzaldehyde, tetra-butyl-
ammonium perchlorate, methyltriphenylphosphonium bromide, t-
chloride,
4-nitrobenzenesulfonyl
Scheme 4. The formation of β-hydroxysufones 4 as side
products.

6
Tetrahedron
BuOK, DBU, KI, NH4I, KBr, NH4Br, Na2SO4, MgSO4,
gradient of the latter from 10 to 50 vol%. The yield when the
ACCEPTED MANUSCRIPT
CH3CN, THF, CH2Cl2, petroleum ether (PE, 40/70) and ethyl
acetate (EA) were purchased from commercial sources and were
used as received. 4-Methoxybenzenesulfonohydrazide (1b), 4-
iodobenzenesulfonohydrazide (1c), 4-bromobenzenesulfono-
hydrazide (1d), 4-chlorobenzenesulfonohydrazide (1e) and 4-
nitrobenzenesulfonohydrazide (1f) were synthesized according to
the literature 75. 1-iso-Propyl-4-vinylbenzene (2e), 1-methoxy-3-
vinylbenzene (2k), 1-methoxy-2-vinylbenzene (2l) and 1-nitro-4-
vinylbenzene (2m) were synthesized via Wittig olefination
reaction was performed with current density 270 mA/cm2 is
reported in the parentheses.
78
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3aa)
.
78
Light-yellow needles, m.p. = 117.0-117.8 °С (lit. m.p. =
117-118 °С (CH2Cl2–hexane)). Yield 387 mg, 93% (374 mg,
90%). Rf = 0.44 (TLC, PE:EA, 5:1). 1H NMR (CDCl3), δ: 2.41 (s,
3H), 6.84 (d, J = 15.4 Hz, 1H), 7.31-7.47 (m, 7H), 7.64 (d, J =
15.4 Hz, 1H), 7.81 (d, J = 8.0 Hz, 2H). 13C NMR (CDCl3), δ:
21.6, 127.5, 127.6, 128.4, 129.0, 129.9, 131.0, 132.4, 137.6,
141.9, 144.3.
according to the literature 76,77
.
Cyclic voltammetry (CV) was performed on an IPC-Pro
computer-assisted potentiostat manufactured by Econix (scan rate
error 1.0%, potential setting 0.25 mV). The experiments were
performed in a 10-mL five-neck glass conic electrochemical cell
with a water jacket for thermostatting. CV curves were recorded
using a three-electrode scheme. The working electrode was a disc
glassy-carbon electrode (d = 1.7 mm). A platinum wire served as
an auxiliary electrode. A saturated calomel electrode was used as
the reference electrode and was linked to the solution by a bridge
with a porous ceramic diaphragm filled with background
electrolyte. The tested solutions were thermostatted at 25±0.5 °С.
In a typical case, 5 mL solution was utilized and the depolarizer
concentration was 2 mmol/L. The working electrode was
polished before recording each CV curve.
78
(E)-1-Methoxy-4-(styrylsulfonyl)benzene (3ba)
.
78
Light-yellow powder, m.p. = 77.5-79.0 °С (lit. m.p. = 75-
76 °С (CH2Cl2–hexane)). Yield 361 mg, 89% (316 mg, 78%). Rf
= 0.26 (TLC, PE:EA, 5:1). H NMR (CDCl3), δ: 3.84 (s, 3H),
6.83 (d, J = 15.4 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 7.36-7.46 (m,
5H), 7.60 (d, J = 15.4 Hz, 1H), 7.85 (d, J = 8.8 Hz, 2H). 13C
NMR (CDCl3), δ: 55.6, 114.5, 127.8, 128.4, 128.9, 129.8, 130.9,
132.0, 132.4, 141.3, 163.5.
1
(E)-1-Iodo-4-(styrylsulfonyl)benzene (3ca).
Light-yellow powder, m.p. = 120.0-121.5 °С. Yield 329 mg,
85% (131 mg, 34%). Rf = 0.53 (TLC, PE:EA, 5:1). H NMR
1
(CDCl3), δ: 6.81 (d, J = 15.4 Hz, 1H), 7.37-7.40 (m, 5H), 7.62-
7.69 (m, 3H), 7.88 (d, J = 8.8 Hz, 2H). 13C NMR (CDCl3), δ:
101.2, 126.7, 128.6, 129.0, 129.1, 131.4, 132.1, 138.6, 140.4,
143.1. Calculated for С14Н11IО2S С: 45.42%, Н: 2.99%, I:
34.28%, S: 8.66%. Found С: 45.48%, Н: 2.91%, I: 34.59%, S:
8.33%. HRMS (ESI) m/z [M+Na]+: Calculated for
[С14Н11INaО2S]+: 392.9417. Found: 392.9407. IR, νmax(KBr)
3430, 1618, 1566, 1385, 1313, 1143, 1082, 1052, 1005, 977, 963,
861, 826, 809, 686, 621, 571, 534 cm-1.
General procedure 1. Optimization of the reaction
conditions for synthesis of 3aa from sulfonyl hydrazide 1a
and styrene 2a (Table 1): An undivided cell was equipped
with a carbon plate anode (5 cm2) and a Fe plate cathode (5
cm2) and connected to a DC regulated power supply. The
solution of p-toluenesulfonyl hydrazide 1a (300 mg, 1.61 mmol),
styrene 2a (1.61-4.83 mmol, molar ratio 1-3 mol 2a/mol 1a) and
supporting electrolyte KI, NH4I, KBr or NH4Br (0.80-4.83 mmol,
molar ratio 0.5-3 mol/mol 1a) in 30 mL of CH3CN-H2O (1:1) or
THF-H2O (1:1) was electrolyzed using constant current
conditions (60, 150, 270 mA/cm2) at 30 °C under magnetic
stirring. During electrosynthesis the reaction mixture increases a
temperature, hence external cooling is needed. Then electrodes
were washed with EtOH (2 × 30 mL). The solvent from
combined organic phases was removed under reduced pressure.
The residue was diluted with EtOAc (50 mL) and washed with a
saturated aqueous solution of Na2S2O3 (8 mL), brine (2 × 8 mL)
and water (2 × 8 mL), dried over Na2SO4, concentrated under
reduced pressure and dried at 10-20 torr. The desired product 3aa
was isolated by chromatography on SiO2 with elution using PE-
EA in a linear gradient of the latter from 10 to 50 vol%.
21
(E)-1-Bromo-4-(styrylsulfonyl)benzene (3da)
.
21
Light-brown powder, m.p. = 95.7-96.5 °С (lit. m.p. = 98-
100 °С). Yield 319 mg, 79% (266 mg, 66%). Rf = 0.52 (TLC,
PE:EA, 5:1). H NMR (CDCl3), δ: 6.82 (d, J = 15.5 Hz, 1H),
7.36-7.48 (m, 5H), 7.65-7.70 (m, 3H), 7.79 (d, J = 9.1 Hz, 2H).
13C NMR (CDCl3), δ: 126.7, 128.6, 129.1, 129.2, 131.4, 132.1,
132.6, 139.7, 143.1.
1
78
(E)-1-Chloro-4-(styrylsulfonyl)benzene (3ea)
.
78
Light-yellow powder, m.p. = 79.0-81.0 °С (lit. m.p. = 78-
80 °С (CH2Cl2–hexane)). Yield 300 mg, 74% (312 mg, 77%);
275 mg, 68% (1.2 equiv of 2a was used). Rf = 0.50 (TLC, PE:EA,
1
5:1). H NMR (CDCl3), δ: 6.83 (d, J = 15.3 Hz,1H), 7.38-7.52
General procedure 2. Synthesis of vinyl sulfones 3aa-3fa,
3ab-3ap (Table 2). An undivided cell was equipped with a
carbon plate anode (5 cm2) and a Fe plate cathode (5 cm2)
and connected to a DC regulated power supply. The solution
of sulfonyl hydrazide 1a-1f (300 mg, 1.01-1.61 mmol), alkene
2a-2p (1.93-3.22 mmol, molar ratio 1.2 or 2 mol 2/mol 1) and
supporting electrolyte KI (2.02-3.22 mmol, molar ratio 2
mol/mol 1) in 30 mL of THF-H2O (1:1) was electrolyzed using
constant current conditions (60 or 270 mA/cm2) at 30 °C, under
magnetic stirring. During electrosynthesis the reaction mixture is
cooled externally. Then electrodes were washed with EtOH (2 ×
30 mL). The solvent from combined organic phases was removed
under reduced pressure. The residue was diluted with EtOAc (50
mL) and washed with saturated aqueous solution of Na2S2O3 (8
mL), brine (2 × 8 mL) and water (2 × 8 mL), dried over Na2SO4,
concentrated under reduced pressure and dried at 10-20 torr. The
desired products 3aa-3fa, 3ab-3ap were isolated by
chromatography on SiO2 with elution using PE-EA in a linear
(m, 7H), 7.67 (d, J = 15.3 Hz,1H), 7.87 (d, J = 8.2 Hz, 2H). 13C
NMR (CDCl3), δ: 126.8, 128.6, 129.1, 129.6, 131.4, 132.1, 139.2,
140.0, 143.0.
20
(E)-1-Nitro-4-(styrylsulfonyl)benzene (3fa)
.
Orange powder, m.p. = 145.0-147.0 °С (lit. 20 m.p. = 152-154
°С). Yield 72 mg, 18% (196 mg, 49%). Rf = 0.33 (TLC, PE:EA,
5:1). H NMR (CDCl3), δ: 6.85 (d, J = 15.4 Hz,1H), 7.40-7.51
(m, 5H), 7.75 (d, J = 15.4 Hz,1H), 8.13 (d, J = 8.8 Hz, 2H), 8.36
(d, J = 8.8 Hz, 2H). 13C NMR (CDCl3), δ: 124.5, 125.7, 128.8,
129.0, 129.2, 131.8, 131.8, 144.9, 146.6, 150.5.
1
20
(E)-1-Methyl-4-(4-methylstyrylsulfonyl)benzene (3ab)
.
20
White needles, m.p. = 147.5-148.7 °С (lit. m.p. = 152-154
°С). Yield 378 mg, 85% (408 mg, 93%). Rf = 0.45 (TLC, PE:EA,
5:1). 1H NMR (CDCl3), δ: 2.35 (s, 3H), 2.41 (s, 3H), 6.78 (d, J =
15.4 Hz, 1H), 7.16 (d, J = 7.3 Hz, 2H), 7.33 (t, J = 8.8 Hz, 2H),

7
7.60 (d, J = 15.4 Hz, 1H), 7.80 (d, J = 8.8 Hz, 2H). 13C NMR
(CDCl3), δ: 21.4, 21.5, 126.3, 127.6, 128.5, 129.6, 129.7, 129.9,
137.9, 141.6, 141.9, 144.2.
J = 8.8 Hz, 2H). 13C NMR (CDCl3), δ: 21.6, 123.1, 127.2,
ACCEPTED MANUSCRIPT
127.8, 129.3, 130.0, 130.5, 131.0, 133.8, 134.5, 137.4, 140.0,
144.6.
(E)-1-Methoxy-4-(2-tosylvinyl)benzene (3aj) 82
.
79
(E)-1-Methyl-3-(2-tosylvinyl)benzene (3ac)
.
Yellow needles, m.p. = 91.2-92.0 °С (lit. 79 m.p. = 82-83 °С).
Yield 403 mg, 92% (268 mg, 61%). Rf = 0.50 (TLC, PE:EA, 5:1).
1H NMR (CDCl3), δ: 2.37 (s, 3H), 2.45 (s, 3H), 6.86 (d, J = 15.4
Hz, 1H), 7.23-7.30 (m, 4H), 7.36 (d, J = 8.1 Hz, 2H), 7.65 (d, J =
15.4 Hz, 1H), 7.85 (d, J = 8.1 Hz, 2H). 13C NMR (CDCl3), δ:
21.2, 21.6, 125.7, 127.3, 127.6, 128.9, 129.0, 129.9, 131.9, 132.4,
137.8, 138.8, 142.1, 144.3.
Light-brown powder, m.p. = 83.0-84.0 °С (lit. 82 m.p. = 96-97
°С). Yield 232 mg, 50% (200 mg, 43%). Rf = 0.21 (TLC, PE:EA,
5:1). 1H NMR (CDCl3), δ: 2.41 (s, 3 H), 3.81 (s, 3 H), 6.68 (d, J =
15.4 Hz, 1H), 6.87 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H),
7.40 (d, J = 8.1 Hz, 2H), 7.58 (d, J = 15.4 Hz, 1H), 7.80 (d, J =
8.1 Hz, 2H). 13C NMR (CDCl3), δ: 21.5, 55.4, 114.4, 124.8,
125.0, 127.5, 129.8, 130.2, 138.2, 141.7, 144.0, 161.9.
80
(E)-1-Methyl-2-(2-tosylvinyl)benzene (3ad) 80
.
(E)-1-Methoxy-3-(2-tosylvinyl)benzene (3ak)
.
Yellow needles, m.p. = 81.5-82.7 °С (lit. 80 m.p. = 70-71 °С).
Yield 342 mg, 78% (311 mg, 71%). Rf = 0.47 (TLC, PE:EA, 5:1).
1H NMR (CDCl3), δ: 2.42 (s, 3H), 2.43 (s, 3H), 6.76 (d, J = 15.4
Hz, 1H), 7.16-7.42 (m, 6H), 7.82 (d, J = 8.1 Hz, 2H), 7.92 (d, J =
15.4 Hz, 1H). 13C NMR (CDCl3), δ: 19.7, 21.5, 126.4, 126.8,
127.6, 128.5, 129.9, 130.8, 130.9, 131.3, 137.7, 138.0, 139.5,
144.3.
Yellow powder, m.p. = 52.5-54.5 °С. Yield 255 mg, 55%
(325 mg, 70%); 232 mg, 50% (1.2 equiv of 2k was used). Rf =
0.23 (TLC, PE:EA, 5:1). 1H NMR (CDCl3), δ: 2.44 (s, 3 H), 3.81
(s, 3 H), 6.85 (d, J = 15.1 Hz, 1H), 6.94-6.98 (m, 2H), 7.07 (d, J
= 7.3 Hz, 1H), 7.28 (d, J = 7.3 Hz, 1H), 7.34 (d, J = 8.2 Hz, 2H),
7.62 (d, J = 15.1 Hz, 1H), 7.83 (d, J = 8.2 Hz, 2H). 13C NMR
(CDCl3), δ: 21.6, 55.3, 113.3, 117.0, 121.1, 127.7, 127.9, 130.0,
130.0, 133.7, 137.7, 141.8, 144.4, 160.0.
81
(E)-1-Isopropyl-4-(2-tosylvinyl)benzene (3ae)
.
(E)-1-Methoxy-2-(2-tosylvinyl)benzene (3al) 83
.
81
White powder, m.p. = 110.0-111.5 °С (lit. m.p. = 135-136
°С). Yield 460 mg, 95% (421 mg, 87%). Rf = 0.53 (TLC, PE:EA,
5:1). 1H NMR (CDCl3), δ: 1.23 (d, J = 7.3 Hz, 6H), 2.42 (s, 3H),
2.86-2.95 (m, 1H), 6.80 (d, J = 15.4 Hz, 1H), 7.23 (d, J = 8.1 Hz,
2H), 7.32 (d, J = 8.1 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H), 7.63 (d, J
= 15.4 Hz, 1H), 7.81 (d, J = 8.1 Hz, 2H). 13C NMR (CDCl3), δ:
21.5, 23.6, 34.0, 126.5, 127.1, 127.6, 128.6, 129.9, 130.0, 138.0,
142.0, 144.2, 152.5.
83
White powder, m.p. = 79-81 °С (lit.
m.p. = 81-82 °С).
Yield 339 mg, 73% (139 mg, 30%). Rf = 0.17 (TLC, PE:EA, 5:1).
1H NMR (CDCl3), δ: 2.41 (s, 3H), 3.86 (s, 3H), 6.89-6.96 (m,
2H), 7.04 (d, J = 15.4 Hz, 1H), 7.30-7.40 (m, 4H), 7.80-7.88 (m,
3 H). 13C NMR (CDCl3), δ: 21.6, 55.5, 111.2, 120.7, 121.3,
127.6, 128.2, 129.8, 130.7, 132.3, 138.0, 138.2, 144.0, 158.8.
19
(E)-1-Nitro-4-(2-tosylvinyl)benzene (3am)
.
(E)-1-tert-Butyl-4-(2-tosylvinyl)benzene (3af) 20
.
19
Yellow powder, m.p. = 172-174 °С (lit.
m.p. = 167-168
20
White powder, m.p. = 107.5-109.0 °С (lit. m.p. = 125-127
°С). Yield 259 mg, 53% (156 mg, 32%). Rf = 0.13 (TLC, PE:EA,
5:1). 1H NMR (CDCl3), δ: 2.44 (s, 3H), 6.99 (d, J = 15.4 Hz, 1H),
7.36 (d, J = 7.3 Hz, 2H), 7.61-7.70 (m, 3H), 7.82 (d, J = 8.1 Hz,
2H), 8.22 (d, J = 8.1 Hz, 2H). 13C NMR (CDCl3), δ: 21.6, 124.2,
127.9, 129.1, 130.1, 132.0, 136.8, 138.5, 138.6, 145.0, 148.9.
°С). Yield 400 mg, 79% (319 mg, 63%); 354 mg, 70% (1.2 equiv
of 2f was used). Rf = 0.53 (TLC, PE:EA, 5:1). 1H NMR (CDCl3),
δ: 1.29 (s, 9H), 2.41 (s, 3H), 6.79 (d, J = 15.4 Hz, 1H), 7.31 (d, J
= 8.1 Hz, 2H), 7.40 (m, 4H), 7.63 (d, J = 15.4 Hz, 1H), 7.80 (d, J
= 8.1 Hz, 2H). 13C NMR (CDCl3), δ: 21.5, 31.0, 34.9, 126.0,
126.5, 127.6, 128.4, 129.6, 129.9, 137.9, 141.9, 144.2, 154.8.
(E)-1,2,3,4,5-Pentafluoro-6-(2-tosylvinyl)benzene (3an).
Light-brown powder, m.p. = 123.0-124.7 °С. Yield 247 mg,
44% (432 mg, 77%); 196 mg, 35%, (1.2 equiv of 2n was used).
Rf = 0.63 (TLC, PE:EA, 5:1). 1H NMR (CDCl3), δ: 2.44 (s, 3H),
7.19 (d, J = 15.8 Hz, 1H), 7.36 (d, J = 8.1 Hz, 2H), 7.63 (d, J =
15.8 Hz, 1H), 7.80 (d, J = 8.1 Hz, 2H). 13C NMR (CDCl3), δ: 21.4
20
(E)-1-Chloro-4-(2-tosylvinyl)benzene (3ag)
.
20
White needles, m.p. = 146.5-147.7 °С (lit. m.p. = 149-151
°С). Yield 438 mg, 93% (410 mg, 87%). Rf = 0.47 (TLC, PE:EA,
5:1). 1H NMR (CDCl3), δ: 2.42 (s, 3 H), 6.81 (d, J = 15.2 Hz,
1H), 7.32 (m, 6H), 7.58 (d, J = 15.2 Hz, 1H), 7.80 (d, J = 8.2 Hz,
2H). 13C NMR (CDCl3), δ: 21.6, 127.7, 128.2, 129.3, 129.6,
130.0, 130.9, 137.0, 137.4, 140.4, 144.5.
3
(s), 108.0 (dt,2JC-F=13.3 Hz, JC-F=4.4 Hz), 125.0 (m), 127.8 (s),
3
1
130.00 (s), 135.5 (tm, JC-F=8.5 Hz), 136.3 (s), 137.6 (dm, JC-
F=250.2 Hz),142.1 (dm,1JC-F=246.2 Hz), 145.0 (s), 145.5 (dm,1JC-
F=259.3 Hz). 19F NMR (CDCl3), δ: -161.94 (tm, J=21.1 Hz, 2F), -
150.22 (t, J=20.1 Hz, F), -139.34 (d, J=16.9 Hz, 2F). Calculated
for С15Н9F5О2S С: 51.73%, Н: 2.60%, S: 9.21%. Found С:
51.64%, Н: 2.44%, S: 9.08%. HRMS (ESI) m/z [M+Na]+:
Calculated for [С15Н9F5NaО2S]+: 371.0136. Found: 371.0130. IR,
νmax(KBr) 3433, 1654, 1622, 1595, 1528, 1500, 1421, 1324,
1309, 1302, 1290, 1209, 1148, 1084, 1005, 972, 966, 850, 814,
760, 672, 644, 629, 581, 551, 532, 457, 407 cm-1.
82
(E)-1-Fluoro-4-(2-tosylvinyl)benzene (3ah)
.
Brown powder, m.p. = 87.8-88.9 °С (lit. 82 m.p. = 90-91 °С).
Yield 271 mg, 61% (289 mg, 65%). Rf = 0.42 (TLC, PE:EA, 5:1).
1H NMR (CDCl3), δ: 2.42 (s, 3H), 6.77 (d, J = 15.4 Hz, 1H), 7.06
(t, J = 8.8 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.43-7.48 (m, 2H),
7.60 (d, J = 15.4 Hz, 1H), 7.81 (d, J = 8.0 Hz, 2H). 13C NMR
2
(CDCl3), δ: 21.6, 116.2 (d, JC-F = 22.6 Hz), 116.4, 127.4, 127.7,
4
3
128.8 (d, JC-F = 3.3 Hz), 130.0, 130.5 (d, JC-F = 9 Hz), 137.6,
84
(E)-1-Methyl-4-(2-phenylprop-1-enylsulfonyl) benzene (3ao)
.
140.6, 144.4, 164.2 (d, JC-F = 253.6 Hz). 19F NMR (CDCl3), δ: -
1
84
108.75.
White needles, m.p. = 86.0-88.0 °С (lit. m.p. = 96.5-97.0
°С
0.40 (TLC, PE:EA, 5:1). 1H NMR (CDCl3), δ: 2.43 (s, 3H), 2.51
(s, 3H), 6.58 (s, 1H), 7.23-7.35 (m, 7H), 7.83-7.85 (m, 2H). 13
NMR (CDCl3), δ: 17.1, 21.6, 126.3, 127.3, 127.8, 128.7, 129.8,
129.8, 139.3, 140.2, 144.1, 152.9.
(hexane—EtOAc)). Yield 140 mg, 32% (22 mg, 5%). Rf =
(E)-1-Bromo-3-(2-tosylvinyl)benzene (3ai) 81
.
81
C
White powder, m.p. = 88.0-89.5 °С (lit.
m.p. = 99 °С).
Yield 489 mg, 90% (472 mg, 87%). Rf = 0.42 (TLC, PE:EA, 5:1).
1H NMR (CDCl3), δ: 2.43 (s, 3H), 6.84 (d, J = 15.4 Hz, 1H),
7.22-7.27 (m, 1H), 7.33-7.39 (m, 3H), 7.50-7.60 (m, 3H), 7.81 (d,
85
(E)-1-Methyl-4-(2-(octylsulfonyl)vinyl)benzene (3ap)
.

8
Tetrahedron
ACCEPTED MANUSCRIPT
Colourless liquid. Yield 107 mg, 25% (21 mg, 5%). Rf =
saturated aqueous solution of Na2S2O3 (15 mL), brine (2×15 mL)
1
0.40 (TLC, PE:EA, 10:1). H NMR (CDCl3), δ: 0.79-0.81 (m,
3H), 1.15-1.30 (m, 6H), 1.38-1.40 (m, 2H), 2.11-2.19 (m, 2H),
2.37 (s, 1H), 6.26 (d, J = 14.6 Hz, 1H), 6.86-6.96 (m, 1H) 7.27
(d, J = 7.5 Hz, 2H), 7.70 (d, J = 7.5 Hz, 2H). 13C NMR (CDCl3),
δ: 13.7, 21.3, 22.2, 27.3, 28.4, 31.2, 127.3, 129.6, 130.4, 137.6,
143.9, 146.4.
and water (2×15 mL), dried over Na2SO4, concentrated under
reduced pressure and dried at 10-20 torr. The residue was
recrystallized from ethanol to give pure product 3aa in 93% (3.87
g) yield.
86
1-(4-Methoxyphenyl)-2-tosylethanol (4aj)
.
Acknowledgments
White powder, m.p. = 65-67 °С. Yield 202 mg, 41% (163
mg, 33%). Rf = 0.59 (TLC, PE:EA, 2:1). H NMR (CDCl3), δ:
This work was supported by the Russian Science Foundation
(Grant 17-73-10364).
1
2.45 (s, 3H), 3.28 (dd, J = 14.0, 1.5 Hz, 1 H), 3.46 (dd, J = 14.0,
10.1 Hz, 1 H), 3.75 (s, 3H), 5.17 (dd, J = 10.1, 1.5 Hz, 1H), 6.82
(d, J = 8.8 Hz, 2H), 7.18 (d, J = 8.8 Hz, 2H), 7.36 (d, J = 8.1 Hz,
2H), 7.81 (d, J = 8.1 Hz, 2H). 13C NMR (CDCl3), δ: 21.6, 55.2,
63.9, 68.1, 114.0, 126.9, 128.0, 130.0, 132.8, 136.2, 145.1, 159.5.
References and notes
1. Frankel BA, Bentley M, Kruger RG, McCafferty DG. J.
Am. Chem. Soc. 2004; 126:3404.
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Knox AJ. J. Med. Chem. 2013; 56:6638.
1-[(4-Methylphenyl)sulfonyl]-2-phenylpropan-2-ol (4ao) 87
.
87
White powder, m.p. = 99.5-100.5 °С (lit. m.p. = 103–104
°C (Et2O)). Yield 173 mg, 37% (140 mg, 30%). Rf = 0.64 (TLC,
PE:EA, 2:1). 1H NMR (CDCl3), δ: 1.71 (d, J = 1.1 Hz, 3 H), 2.39
(s, 3 H), 3.61 (dd, J = 14.6, 1.1 Hz, 1 H), 3.72 (dd, J = 14.6, 1.1
Hz, 1 H), 4.66 (br s, 1 H), 7.14-7.24 (m, 5 H), 7.26-7.34 (m, 2 H),
7.49 (d, J = 8.2 Hz, 2 H). 13C NMR (CDCl3), δ: 21.5, 30.7, 66.6,
73.0, 124.5, 127.0, 127.4, 128.1, 129.6, 137.3, 144.4.
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mL). Subsequently, the two solutions were mixed to generate p-
toluenesulfonyl iodide (a yellow precipitate). After the reaction
for 1 h, the yellow precipitate was filtered and recrystallized from
CCl4.
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methyl-4-(2-phenylprop-1-enylsulfonyl) benzene 3ao. An
undivided cell was equipped with a carbon plate anode (5
cm2) and a Fe plate cathode (5 cm2) and connected to a DC
regulated power supply. The solution of β-hydroxysulfone 4ao
(200 mg, 0.69 mmol), supporting electrolyte KI (1.38 mmol,
molar ratio 2 mol/mol 1) in 30 mL of THF-H2O (1:1) was
electrolyzed using constant current conditions (60 mA/cm2) at 30
°C under magnetic stirring. During electrosynthesis the reaction
mixture was externally cooled. Then electrodes were washed
with EtOH (2 × 30 mL). The solvent from combined organic
phases was removed under reduced pressure (10-20 torr). The
residue was diluted with EtOAc (50 mL) and washed with
saturated aqueous solution of Na2S2O3 (8 mL), brine (2 × 8 mL)
and water (2 × 8 mL), dried over Na2SO4, concentrated under
1
reduced pressure and dried at 10-20 torr. According to H NMR
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