N,N′-Disulfonylhydrazines: New sulfonylating reagents for highly efficient synthesis of (E)-vinyl sulfones at room temperature

Article abstract of DOI:10.1016/j.tet.2020.131019

N,N′-Disulfonylhydrazines have been proven to be the most reactive precursors of sulfonyl radicals in all types of sulfonyl substituted hydrazines as early as a half century ago. But such function has not been applied in organic synthesis except the formation of disulfones by self-dimerization of sulfonyl radicals. In this article, they were introduced as new sulfonylating reagents and their combinations with NIS and Et₃N were established as excellent iodosulfonylating reagents for alkenes. Finally, a highly efficient method for the synthesis of (E)-vinyl sulfones was developed by mixing an alkene, a N,N′-disulfonylhydrazine, NIS and Et₃N in THF at room temperature for 5 min.

Full text of DOI:10.1016/j.tet.2020.131019

Journal Pre-proof
N,N′-disulfonylhydrazines: New sulfonylating reagents for highly efficient synthesis of
(E)-Vinyl sulfones at room temperature
Dongping Luo, Lin Min, Weiping Zheng, Lidong Shan, Xinyan Wang, Yuefei Hu
PII:
S0040-4020(20)30121-6
https://doi.org/10.1016/j.tet.2020.131019
TET 131019
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 29 November 2019
Revised Date: 12 January 2020
Accepted Date: 3 February 2020
Please cite this article as: Luo D, Min L, Zheng W, Shan L, Wang X, Hu Y, N,N′-disulfonylhydrazines:
New sulfonylating reagents for highly efficient synthesis of (E)-Vinyl sulfones at room temperature,
Tetrahedron (2020), doi: https://doi.org/10.1016/j.tet.2020.131019.
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N,N’-Disulfonylhydrazines: New Sulfonylating
Reagents for Highly Efficient Synthesis of (E)-
Vinyl Sulfones at Room Temperature
Leave this area blank for abstract info.
Dongping Luo,a Lin Min,a Weiping Zheng,a Lidong Shan,a Xinyan Wanga,* and Yuefei Hua,*
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education),
Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
O O
S
NIS, NEt3, THF, rt, 5 min
25 samples in 21-95%
(Ar1SO2NH)2
+
ArCH=CH2
Ar
Ar1

1
Tetrahedron
journal homepage: www.elsevier.com
N,N’-Disulfonylhydrazines: New Sulfonylating Reagents for Highly Efficient
Synthesis of (E)-Vinyl Sulfones at Room Temperature
Dongping Luo,a Lin Min,a Weiping Zheng,a Lidong Shan,a Xinyan Wanga,* and Yuefei Hua,*
a Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing
100084, P. R. China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
N,N’-Disulfonylhydrazines have been proven to be the most reactive precursors of sulfonyl
radicals in all types of sulfonyl substituted hydrazines as early as a half century ago. But such
function has not been applied in organic synthesis except the formation of disulfones by self-
dimerization of sulfonyl radicals. In this article, they were introduced as new sulfonylating
reagents and their combinations with NIS and Et3N were established as excellent
iodosulfonylating reagents for alkenes. Finally, a highly efficient method for the synthesis of
(E)-vinyl sulfones was developed by mixing an alkene, a N,N’-disulfonylhydrazine, NIS and
Et3N in THF at room temperature for five minutes.
Available online
Keywords:
Alkynes
Radical reactions
N,N’-disulfonylhydrazines
Vinyl sulfones
Sulfonyl radicals
.
1. Introduction
replacement of RSO2I (2a) with a combination of a sulfonylating
reagent [such as R1SO2H (2b),[10] TosMIC (2c, p-tolylsulfonyl-
methyl isocyanide),[11] R1SO2Na (2d)[12] or R1SO2NHNH2 (2e),[13]
etc.], an iodine-source and an oxidant (Scheme 2b). Depending
upon the conditions, these procedures were performed via a two-
step or a two-step one-pot process.
(E)-Vinyl sulfones have unique conjugated structures. Many of
them have demonstrated novel bioactivities[1] and most of them
have used as versatile synthons in organic synthesis.[2] As shown
in Scheme 1, their double-bond and sulfone groups are
responsible for numerous transformations, such as: (a) Michael
addition;[3] (b) [2+n] cycloaddition;[4] (c) epoxidation;[5] and (d)
desulfonylative coupling,[6] etc.
I
R1 base reagent
dehydroiodination
R
R1
RCH=CH2 (1)
R1SO2I
S
(a)
S
iodosulfonylation
O
O
O O
R
2a
X
Y 1-3
O
3
(E)-vinyl sulfones
(b) [2+n] cycloaddition
X, Y = C-, N-, O-
(c) epoxidation
R1SO2H (2b)
R
R
R1
R1
RCH=CH2 (1)
[I]-source, oxidant
R
S
S
O
O
O
O
TosMIC (2c)
(b)
(c)
iodosulfonylation
R1SO2Na (2d)
R1SO2NHNH2 (2e)
(d) desulfonylative coupling
R
R1
(a) Michael addition
S
Nu-
O
O
R1
S
R
(E)-vinyl sulfones
R2(Ar)
Ar
Ar1
NIS, NEt3, THF, rt, 5 min
(Ar1SO2NH)2
O
O
+
S
ArCH=CH2
Nu
this work
O
O
1
5
4
Scheme 1. (E)-Vinyl sulfones as versatile synthons.
Scheme 2. Existing procedures and this work.
Numerous methods have been developed for the synthesis of
(E)-vinyl sulfones and have been well-reviewed in literature.[2d-e,7]
Prominent among them are the methods that employ the
iodosulfonylation of an alkene (1) as a key step due to their
reliability and practicability. In the early reported procedures,[8]
the iodosulfonylation proceeded by using RSO2I (2a) as both a
sulfonylating reagent and an iodine-source (Scheme 2a).
However, these most straightforward procedures were modified
soon due to the highly chemical instability of RSO2I (2a).[9] Later,
many modified procedures have been developed by the
Although each existing procedure has its own advantages, it
also has its own unavoidable drawbacks. For example, the salt
RSO2Na (2d) is the most often used reagent for such purpose but
it suffered from the poor solubility in organic solvents. Compared
to other sulfonylating reagents, the procedures mediated by
RSO2NHNH2 (2e)[13] have been developed rapidly in recent
years. However, many of them suffered from the use of peroxides
as oxidants under heating or neat conditions. Herein, we
introduce the commercially available N,N’-disulfonylhydrazines

2
Tetrahedron
(4) as a new type of sulfonylating reagents for such purpose. As
Br (9) may come from the capture of ArSO2· by a radical
acceptor Br· (generated in situ from Br2 and NBS); (c) ArSO2·
may be captured similarly by other radical acceptors.
shown in Scheme 2c, (E)-β-arylvinyl arenesulfones (5) were
synthesized efficiently by simply mixing an alkene (1), a N,N’-
disulfonyl-hydrazine (4), NIS (N-iodosuccinimide) and NEt3
together for 5 min at room temperature.
Br2 or NBS
96% aq. MeCN, rt
TsNHNHTs
Ts Ts
+
Ts Br
+
Ts OH
2. Results and Discussion
4a
6a
10%
10%
9
57%
53%
10
20%
25%
Br2:
NBS:
The mechanism studies for the procedures mediated by
sulfonylating reagents 2a-2e indicated that the conversion of an
alkene (1) into an β-iodoethyl sulfone (3) by iodosulfonylation is
the key step.[8,10-13] As shown in Scheme 3a, the iodo-
sulfonylation of an alkene (1) went through a radical addition
pathway and was initiated by a sulfonyl radical (RSO2·).
Therefore, how to conveniently and efficiently generate a
sulfonyl radical (RSO2·) has been a key issue for the synthesis of
Scheme 4 Two experiments for the formation of the by-product 9.
Thus, we hypothesized that the β-iodoethyl sulfone (3) may be
synthesized from an alkene (1, as a radical acceptor) and
(ArSO2NH)2 (4, as a precursor of ArSO2·) when NIS (a precursor
of HOI and I·) is used as an alternative for NBS. To prove this
hypothesis, a group of experiments were tested by using
PhCH=CH2 (1a) and TsNHNHTs (4a) as model substrates. As
shown in Table 1, the desired product 2-iodo-2-phenylethyl 4-
methylphenyl sulfone (3a) was obtained in 7% yield after the
mixture of 1a and 4a was treated by NIS for 2 h in anhydrous
MeCN (entry 1). As was expected, when the same reaction
proceeded in aqueous MeCN (96 vol%), the N2 was released
from 4a instantaneously to give 3a in 85% yield within 5 min
(entry 2). In this reaction, a by-product 2-phenylethenyl 4-
methylphenyl sulfone (5a) was also isolated in 10% yield, which
came from the dehydroiodination of 3a. To our delight, the
product 5a was obtained as a single product in 90% yield by
adding three equiv of NEt3 (entry 3) into the reaction system.
Similar excellent yield of 5a was obtained when the reaction
proceeded in anhydrous MeCN in the presence of NEt3 (entry 4),
(E)-vinyl sulfones. Based on this opinion, we made
a
comprehensive investigation for the reagents that can be used to
generate the sulfonyl radicals. We luckily found that, as early as
in 1970, N,N’-disulfonylhydrazines (4)[14] have been proven to be
the most reactive precursors of sulfonyl radicals in all types of N-
sulfonyl substituted hydrazines. As shown in Scheme 3b, the
disulfone Ts-Ts (6a) was synthesized in 52% yield when
TsNHNHTs (4a)[15c] was treated by HNO3 at room temperature
for 1 h, while the disulfone PhSO2SO2Ph (6b) was produced in
41% yield when (PhSO2NH)2 (4b)[15b] was treated by NaOCl at 0
oC for 5 min. A two-step pathway[14a] was proposed for these
conversions: (i) N,N’-disulfonylhydrazines (4a and 4b) were
oxidized to give a highly unstable azo-intermediate (7), which
was then spontaneously decomposed into two sulfonyl radicals
(8); (ii) under the control of the solvent-cage-effect, the sulfonyl
radicals (8) were dimerized into the disulfones 6a or 6b.
which indicated that the oxidation ability of NIS can be enhanced
[17]
by NEt3
like H2O. The results in entries 5-9 indicated that
many solvents were suitable for this conversion. Toluene was the
worst solvent due to its poor solubility for the substrates 4a and
NIS (entry 5), while THF was the best solvent to give 5a in 94%
yield (entry 9). None of 5a was detected in the absence of NIS
(entry 12).
hv, [M]-catalyst
or oxidation
1
R
.
RCH=CH (1)
I
2
.
R
1
S
O
.
(a) 2a-2e
R SO
3
2
radical formation
radical addition
O
Conc. HNO3, rt, 1 h
4a/6a: Ar = p-tolyl, 52%
O
O
NHNH S Ar
O
O
O
S
Table 1. Effects of the solvents on the products of 3a and 5a.a
(b)
Ar
S
Ar
S
Ar
NaOCl, CHCl3, 0 oC, 5 min
O
O
O
NIS, Et3N
solvent, rt, time
4a and 4b
6a and 6b
4b/6b: Ar = Ph, 41%
I
Ts
Ph
+
+
PhCH=CH2
1a
TsNHNHTs
4a
(i) oxidation
(ii) dimerization
Ts
Ph
O
S
O
O
S
O
3a
5a
.
.
Ar
Ar S
O
N
N
Ar
S
Ar
O
O
N
2
O
entry
solvent
NEt3
Time
(min)
3a
5a
(%)b
7
(%)b
trace
10
7
8
1
2c
3
MeCN
without
without
with
120
5
Scheme 3. N,N’-Disulfonylhydrazines (4) as precursors of
sulfonyl radicals.
96% aq. MeCN
96% aq. MeCN
MeCN
PhMe
85
0
5
90
4
with
5
0
90
The investigation also indicated that N,N’-disulfonylhydra-
zines (4) have several important synthetic applications in the past
decades. Almost without exception, these works focused on the
C-N bond formation by N-alkylations of compounds 4.[16]
Surprisingly, compounds 4 have not been applied as the
precursors of sulfonyl radicals (8) except the formation of
disulfones in past half a century. This phenomenon may be
caused by the negative influence of the solvent-cage-effect of the
radical reaction. However, our attention was drawn by one by-
product in an article[14a] as shown in Scheme 4: when TsNHNHTs
(4a) was treated by Br2 or by NBS, the by-product Ts-Br (9) was
generated as a major product instead of the expected Ts-Ts (6a).
Since H2O was necessary for these experiments, HOBr was
proposed to be generated in situ from Br2 and NBS as a “real
oxidant”. Thus, we made three assumptions based on these
results: (a) the “solvent-cage-effect” for the dimerization of
ArSO2· may be broken by using a strong radical acceptor; (b) Ts-
5
with
120
5
0
63
6
DCE
with
0
80
7
DCM
with
5
0
88
8
acetone
THF
with
5
0
90
9
with
5
0
94
10d
11e
12f
THF
with
5
0
61
THF
with
5
0
90
THF
with
120
0
0
a The mixture of 1a (0.5 mmol) and 4a (0.5 mmol) in a solvent (2 mL) was
treated by NIS (1 mmol) with or without Et3N (1.5 mmol) at room
temperature for given times.
b The isolated yields.
c aq. MeCN (96 vol%) was used in the reference [14a].
d 4a (0.25 mmol) was used.
e 4a (0.4 mmol) was used.
f The reaction without NIS.

3
Next, the different tertiary amines and halogen-sources were
tested. As shown in Table 2, many amines could be used as the
activators[17] for NIS with significant differences. The pyridine
derivatives and DIPEA (entries 1-3) were poor activators for this
conversion. DABCO and TMG (entries 4-5) were good
activators, while DBU and NEt3 (entries 6-7) were excellent
activators. The results in entries 8-10 proved that I2, NBS or NCS
could not be used as an alternative for NIS. As was expected,
none of the product 5a was obtained when TBAI and I2O5 were
used as iodine sources because they are not suitable precursors of
iodine radical (entries 10-11).
since it could not be converted into the product 5a under the
standard conditions. None of the product 5a was detected in the
presence of one equiv of TEMPO (Scheme 6e).
NIS, Et3N,THF
O
S
O
rt, 5 min
21-95%
+
ArCH=CH2
(Ar1SO2NH)2
Ar
Ar1
1a-1l
4a-4g
5a-5y
N
Ts
Ts
5a, R = H,
94%
5b, R = 4-Me, 94%
5c, R = 4-t-Bu, 95%
5d, R = 4-OMe, 72%
5e, R = 4-F,
5f, R = 4-Cl,
5g, R = 3-Cl,
5h, R = 2-Cl,
5i, R = 4-Br,
Table 2. Effects of amines and halogen-sources on the formation
of 5a.a
Ts
5j, 95%
5k, 95%
86%
80%
86%
90%
87%
R
amine, [X]-source
THF, rt, 5 min
N
Ph
+
PhCH=CH2
TsNHNHTs
Ts
15-94%
O
S
O
1a
4a
5a
Ph
5l, R = H,
5m, R = 4-Me, 93%
95%
5n, R = 4-t-Bu, 94%
5o, R = 4-Cl, 85%
entry
amine
[X]-source
NIS
5a (%)b
15
43
72
81
88
92
94
63
20
10
0
R
1
2
pyridine
DIPEA
DMAP
DABCO
TMG
DBU
NIS
O
O
O
O
O
O
5p, R = 4-F, 93%
5q, R = 4-Cl, 95%
5r, R = 4-Br, 86%
5s, R = 4-NO2, 82%
3
NIS
S
S
Ph
Ph
Ph
4
NIS
R
R
5t, 91%
5
NIS
6
NIS
Me
Me
O
7
NEt3
NIS
O
5u, R = 4-Me, 33%
5v, R = H,
5w, R = 4-F,
5x, R = 4-NO2, 32%
S
S
21%
34%
8
NEt3
I2
Ph
9
NEt3
NBS
NCS
TBAI
I2O5
5y, 25%
10
11
12
NEt3
NEt3
Scheme 5. The scopes of substrates and products.
NEt3
0
a The mixture of 1a (0.5 mmol) and 4a (0.5 mmol) in THF (2 mL) was treated
by a halogen-source (1 mmol) with an amine (1.5 mmol).
b The isolated yields.
Et N, THF, rt, 5 min
3
recovery of 4a
recovery of 4a
(a)
(b)
97%
NIS, THF, rt, 5 min
96%
Thus far, we realized that we have discovered a new method
for highly efficient synthesis of (E)-vinyl sulfones (5). To
generalize this method, the scopes of substrates and products
were tested under standard conditions (Scheme 5). By fixing
TsNHNHTs (4a), different products 5a-5k were obtained from 2-
arylethenes 1a-1k in high to excellent yields. The substituents on
aromatic rings of 1a-1k showed significant electronic effects, by
which 5a (with strong electron-donating-group –OMe) was
obtained in relatively lower yield. Both products 5j and 5k were
obtained in excellent yields from 2- and 4-vinylpyridines (1j and
1k), respectively. By fixing 2-phenylethene (1a), all tested
disulfonylhydrazines 4a-4g proved to be highly efficient sulfonyl
reagents to give the desired products 5p-5t in good to excellent
yields. The comparable electronic effects were observed, by
which 5s (with strong electron-withdrawing-group –NO2) was
obtained in relatively lower yield. Like most existing procedures,
1,1-disubstituted ethenes showed poor reactivity and the internal
alkenes were not suitable substrates for this method. For
example, the products 5u-5y were synthesized in 21-34% yields
from 1-methyl-1-phenylethene (1l), even though they were
purified easily. Under standard conditions, the product 5a was
synthesized in 91% yield on 2-gram scales.
TsNHNHTs
4a
NIS, Et N, THF, rt, 5 min
3
(c)
(d)
Ts Ts + Ts S Tol
6a,15%
100% conversion
5%
standard conditions
Ts
+
Ts Ts
PhCH=CH
X
2
Ph
Ph
5a
1a
6a
TEMPO (1 equiv)
standard conditions
Ts
(e)
+
PhCH=CH
TsNHNHTs
X
2
1a
4a
5a
Scheme 6. Further control experiments.
Thus, a possible pathway for our method was proposed as
shown in Scheme 7. Initially, Et3N carried out a nucleophilic
attack on the iodine atom of NIS to form Et3N·NIS complex by
halogen bonds,[18] which was then activated into a more oxidative
(or more electrophilic) species Et3N+I.[17] Next, N,N’-
disulfonylhydrazine (4) was oxidized by Et3N+I into the azo-
intermediate (7), which decomposed spontaneously to form
sulfonyl radicals (8) by the release of N2. After the sulfonyl
radical (8) took a radical addition with an arylethene (1), the in
situ formed new radical species 11 was captured by an iodine
radical (generated from NIS) to give β-iodoethyl sulfone (3).
Finally, β-iodoethyl sulfone (3) underwent a dehydroiodination
promoted by Et3N to give the target product 5. The pathway
clearly indicated that NIS functioned as dual precursors of the
More control experiments were tested to further understand the
mechanism. As shown in Scheme 6a-6b, no N2 was released
when TsNHNHTs (4a) was treated with NIS or NEt3 alone.
However, N2 was released quickly and the reaction completed
within five minutes when TsNHNHTs (4a) was treated by the
combination of NIS and NEt3 (Scheme 6c). The results in
Scheme 6d indicated that Ts-Ts (6a) was not an intermediate

4
Tetrahedron
oxidant Et3N+I and the iodine radical, while Et3N functioned as
(CDCl3, 100 MHz) δ 144.4, 141.9, 137.7, 132.4, 131.1, 129.9
dual promoters for the activations of NIS and the
dehydroiodination.
(2C), 129.0 (2C), 128.5 (2C), 127.7 (2C), 127.6, 21.6.
The products 5b-5y were prepared by the similar procedure.
4.2.1. (E)-4-Methylphenyl 2-(4-
methylphenyl)ethenyl sulfone (5b).
O
Ar
Ar
H
N
O
S
O
S
S
1
1
Ar
N
H
Ar
N
5
O O
White solid (128 mg, 94%), mp 151–153 °C (lit.[19a] 152–154
oC); 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 8.0 Hz, 2H), 7.62
(d, J = 15.6 Hz, 1H), 7.37–7.32 (m, 4H), 7.18 (d, J = 8.0 Hz, 2H),
6.79 (d, J = 15.6 Hz, 1H), 2.43 (s, 3H), 2.36 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ 144.2, 142.0, 141.7, 137.9, 129.9 (2C),
129.7 (2C), 129.7, 128.5 (2C), 127.6 (2C), 126.4, 21.6, 21.5.
O
O
O
4
.
Et N
3
Et N HI
3
O
O
Et N
N
I
3
.
Et N NIS
Et N
3
I
3
Ar
Ar
O
S
as an oxidant
.
N
H
Et N HI +
3
O O
.
3
I
as an I source
O
ArCH=CH
O
2
.
O
O
S
O
1
I
Ar
1
1
1
1
.
.
S
O O
S
N
N
Ar
S
Ar
Ar
4.2.2. (E)-4-Methylphenyl 2-(4-tert-
butylphenyl)ethenyl sulfone (5c).
Ar
11
O
O
N
2
7
8
White solid (149 mg, 95%), mp 126–127 °C (lit.[19a] 125–127
oC); 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 8.4 Hz, 2H), 7.64
(d, J = 15.6 Hz, 1H), 7.43–7.38 (m, 4H), 7.33 (d, J = 8.0 Hz, 2H),
6.81 (d, J = 15.2 Hz, 1H), 2.42 (s, 3H), 1.31 (s, 9H); 13C NMR
(CDCl3, 100 MHz) δ 154.8, 144.2, 141.9, 137.9, 129.9 (2C),
129.6, 128.4 (2C), 127.6 (2C), 126.5, 126.0 (2C), 34.9, 31.0 (3C),
21.6.
Scheme 7. A proposed pathway for the formation of 5.
3. Conclusions
In conclusion, four items have been included in this article. First,
N,N’-disulfonylhydrazines were introduced as new sulfonylating
reagents for the synthesis of (E)-vinyl sulfones. Second, the
combination of NIS/Et3N was discovered as an excellent oxidant
for the oxidative decomposition of N,N’-disulfonylhydrazines
into sulfonyl radicals. Third, the combinations of N,N’-
disulfonylhydrazine/NIS/Et3N were discovered as excellent
iodosulfonylating reagent of alkenes. Finally, a new method for
highly efficient synthesis of (E)-vinyl sulfones was developed
under extremely simple and mild conditions. Since the
importance of (E)-vinyl sulfones as versatile synthons has been
enhanced significantly in recent years, we may expect that this
method will have widespread applications in organic synthesis.
4.2.3. (E)-4-Methylphenyl 2-(4-
methoxyphenyl)ethenyl sulfone (5d).
White solid (104 mg, 72%), mp 178–180 °C (lit.[12e] 177–180
oC); 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 8.4 Hz, 2H), 7.60
(d, J = 15.2 Hz, 1H), 7.42 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.4
Hz, 2H), 6.89 (d, J = 8.8 Hz, 2H), 6.70 (d, J = 15.6 Hz, 1H), 3.83
(s, 3H), 2.43 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 161.9,
144.1, 141.7, 138.2, 130.3 (2C), 129.9 (2C), 127.5 (2C), 125.0,
124.8, 114.4 (2C), 55.4, 21.6.
4.2.4. (E)-4-Methylphenyl
2-(4-
fluorophenyl)ethenyl sulfone (5e).
White solid (119 mg, 86%), mp 97–99 °C (lit.[19a] 96–98 C);
1H NMR (CDCl3, 400 MHz) δ 7.83 (d, J = 8.0 Hz, 2H), 7.62 (d, J
= 15.2 Hz, 1H), 7.50–7.45 (m, 2H), 7.34 (d, J = 8.0 Hz, 2H),
7.10–7.05 (m, 2H), 6.79 (d, J = 15.2 Hz, 1H), 2.43 (s, 3H); 13C
NMR (CDCl3, 100 MHz) δ 164.2 (d, JCF = 252.0 Hz), 144.4,
140.5, 137.6, 130.5 (d, JCF = 9.0 Hz, 2C), 130.0 (2C), 128.7 (d,
o
4. Experimental Section
4.1. General
All melting points were determined on a Yanaco melting point
apparatus and were uncorrected. IR spectra were recorded as KBr
1
pellets on a Nicolet FT-IR 5DX spectrometer. All spectra of H
JCF = 4.0 Hz), 127.7 (2C) , 127.4 (d, JCF = 2.0 Hz), 116.2 (d, JCF
22.0 Hz, 2C), 21.6.
=
NMR (400 MHz) and 13C NMR (100 MHz) were recorded on a
JEOL JNM-ECA 400 spectrometer in CDCl3. TMS was used as
an internal reference and J values are given in Hz. HRMS were
obtained on a Bruker micrOTOF-Q II spectrometer. PE is
petroleum ether (60–90 oC). All starting materials 1a-1l and 4a-
4g[16a] were purchased directly from suppliers or prepared by
known procedures.
4.2.5. (E)-4-Methylphenyl 2-(4-
chlorophenyl)ethenyl sulfone (5f).
White solid (117 mg, 80%), mp 150–152 °C (lit.[19a] 149–151
oC); 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 8.4 Hz, 2H), 7.60
(d, J = 15.6 Hz, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.36–7.34 (m, 4H),
6.83 (d, J = 15.2 Hz, 1H), 2.43 (s, 3H); 13C NMR (CDCl3, 100
MHz) δ 144.5, 140.4, 137.4, 137.1, 130.9, 130.0 (2C), 129.6
(2C), 129.3 (2C), 128.2, 127.7 (2C), 21.6.
4.2. A typical synthesis of (E)-4-methylphenyl 2-phenylethenyl
sulfone (5a).
To a stirred solution of phenylethene (1a, 52 mg, 0.5 mmol) and
TsNHNHTs (4a, 170 mg, 0.5 mmol) in THF (2 mL) was
sequentially added Et3N (152 mg, 1.5 mmol) and NIS (237 mg, 1
mmol) at room temperature. The release of N2 and the color
change from orange to deep brown were observed immediately.
Five minutes later, the reaction was quenched by adding
saturated aqueous solution of Na2S2O3 (10 mL). The mixture was
extracted by EtOAc (3 x 10 mL) and the combined organic layers
were dried over Na2SO4. After the solvent was removed on a
rotavapor, the residue was purified by a fresh chromatography
(10% EtOAc in PE) to give 121 mg (94%) of the product 5a as
white solid, mp 117–118 °C (lit.[19a] 118–120 oC); 1H NMR
(CDCl3, 400 MHz) δ 7.83 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 15.2
Hz, 1H), 7.48–7.46 (m, 2H), 7.41–7.36 (m, 3H), 7.34 (d, J = 8.0
Hz, 2H), 6.85 (d, J = 15.2 Hz, 1H), 2.43 (s, 3H); 13C NMR
4.2.6. (E)-4-Methylphenyl 2-(3-
chlorophenyl)ethenyl sulfone (5g).
White solid (126 mg, 86%), mp 91–92 °C (lit.[19a] 90–92 C);
o
1H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 8.0 Hz, 2H), 7.58 (d, J
= 15.6 Hz, 1H), 7.45 (s, 1H), 7.38–7.30 (m, 5H), 6.86 (d, J = 15.6
Hz, 1H), 2.44 (s, 3H) ; 13C NMR (CDCl3, 100 MHz) δ 144.6,
140.1, 137.3, 135.1, 134.2, 130.9, 130.3, 130.0 (2C), 129.2,
128.1, 127.8 (2C), 126.7, 21.6.
4.2.7. (E)-4-Methylphenyl 2-(2-
chlorophenyl)ethenyl sulphone (5h).
White solid (132 mg, 90%), mp 104–106 °C (lit.[19a] 103–105
1
oC); H NMR (CDCl3, 400 MHz) δ 8.05 (d, J = 15.6 Hz, 1H),
7.84 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.0 Hz, 1H), 7.42 (d, J = 7.6
Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H), 7.33–7.31 (m, 1H), 7.27–7.24

5
(m, 1H), 6.89 (d, J = 15.6 Hz, 1H), 2.44 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ 144.6, 137.8, 137.3, 135.2, 131.8, 130.8,
130.3 (2C), 130.0 (2C), 128.2, 127.8 (2C), 127.2, 21.6.
4.2.15. (E)-4-Fluorophenyl
sulfone (5p).
2-phenylethenyl
White solid (122 mg, 93%), mp 81–83 °C (lit.[19a] 80–82 C);
1H NMR (CDCl3, 400 MHz) δ 7.99–7.94 (m, 2H), 7.68 (d, J =
15.6 Hz, 1H), 7.51–7.46 (m, 2H), 7.45–7.37 (m, 3H), 7.25–7.19
(m, 2H), 6.85 (d, J = 15.2 Hz, 1H); 13C NMR (CDCl3, 100 MHz)
δ 165.6 (d, JCF = 254.0 Hz), 142.6, 136.8 (d, JCF = 3.0 Hz), 132.2,
131.3, 130.5 (d, JCF = 9.0 Hz, 2C), 129.1 (2C), 128.6 (2C), 127.1,
116.6 (d, JCF = 22.0 Hz, 2C).
o
4.2.8. (E)-4-Methylphenyl 2-(4-
bromophenyl)ethenyl sulfone (5i).
White solid (147 mg, 87%), mp 160–162 °C (lit.[19a] 162–164
oC); 1H NMR (CDCl3, 400 MHz) δ 7.82 (d, J = 8.4 Hz, 2H), 7.59
(d, J = 15.2 Hz, 1H), 7.52 (d, J = 8.4 Hz, 2H), 7.36–7.32 (m, 4H),
6.85 (d, J = 15.6 Hz, 1H), 2.44 (s, 3H); 13C NMR (CDCl3, 100
MHz) δ 144.5, 140.4, 137.4, 132.3 (2C), 131.3, 130.0 (2C), 129.8
(2C), 128.3, 127.7 (2C), 125.4, 21.6.
4.2.16. (E)-4-Chlorophenyl 2-phenylethenyl sulfone
(5q).
White solid (132 mg, 95%), mp 83–84 °C (lit.[19a] 82–84 C);
o
4.2.9. (E)-4-Methylphenyl 2-(2-pyridinyl)ethenyl
sulfone (5j).
1H NMR (CDCl3, 400 MHz) δ 7.90–7.87 (m, 2H), 7.69 (d, J =
15.2 Hz, 1H), 7.54–7.47 (m, 4H), 7.45–7.37 (m, 3H), 6.84 (d, J =
15.6 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 143.0, 140.0,
139.2, 132.1, 131.4, 129.6 (2C), 129.1 (4C), 128.6 (2C), 126.8.
White solid (123 mg, 95%), mp 92–94 °C (lit.[12a] 91.8–93.4
oC); 1H NMR (CDCl3, 400 MHz) δ 8.60 (d, J = 4.4 Hz, 1H), 7.84
(d, J = 8.4 Hz, 2H), 7.73 (td, J = 1.6, 7.6 Hz, 1H), 7.62 (d, J =
15.2 Hz, 1H), 7.46–7.39 (m, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.30–
7.27 (m, 1H), 2.43 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 151.0,
150.2, 144.5, 140.0, 137.2, 137.0, 132.1, 129.9 (2C), 127.9 (2C),
125.3, 124.9, 21.6.
4.2.17. (E)-4-Bromophenyl 2-phenylethenyl sulfone
(5r).
White solid (139 mg, 86%), mp 102–103 °C (lit.[12a] 101.2–
o
1
102.6 C); H NMR (CDCl3, 400 MHz) δ 7.81 (d, J = 8.4 Hz,
2H), 7.71–7.67 (m, 3H), 7.50–7.47 (m, 2H), 7.46–7.37 (m, 3H),
6.84 (d, J = 15.2 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 143.1,
139.7, 132.6 (2C), 132.1, 131.4, 129.2 (2C), 129.1 (2C), 128.6
(3C), 126.7.
4.2.10. (E)-4-Methylphenyl 2-(4-pyridinyl)ethenyl
sulfone (5k).
Grey solid (123 mg, 95%), mp 102–104 °C (lit.[12b] 98–100
oC); 1H NMR (CDCl3, 400 MHz) δ 8.66 (d, J = 6.0 Hz, 2H), 7.84
(d, J = 8.0 Hz, 2H), 7.58 (d, J = 15.6 Hz, 1H), 7.37 (d, J = 8.0
Hz, 2H), 7.33 (d, J = 6.4 Hz, 2H), 7.05 (d, J = 15.6 Hz, 1H), 2.45
(s, 3H); 13C NMR (CDCl3, 100 MHz) δ 150.7 (2C), 145.0, 139.6,
138.7, 136.6, 132.5, 130.1 (2C), 127.9 (2C), 122.0 (2C), 21.6.
4.2.18. (E)-4-Nitrophenyl 2-phenylethenyl sulfone
(5s).
Yellowish solid (119 mg, 82%), mp 151–152 °C (lit.[19a] 152–
154 oC); 1H NMR (CDCl3, 400 MHz) δ 8.39 (d, J = 8.8 Hz, 2H),
8.15 (d, J = 8.8 Hz, 2H), 7.77 (d, J = 15.6 Hz, 1H), 7.52–7.40 (m,
5H), 6.86 (d, J = 15.6 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ
150.5, 146.5, 144.9, 131.9, 131.8, 129.2 (2C), 129.0 (2C), 128.8
(2C), 125.6, 124.5 (2C).
4.2.11. (E)-Phenyl 2-phenylethenyl sulfone (5l).
o
White solid (116 mg, 95%), mp 67–68 °C (lit.[19a] 67–69 C);
1H NMR (CDCl3, 400 MHz) δ 7.97–7.94 (m, 2H), 7.69 (d, J =
15.6 Hz, 1H), 7.64–7.60 (m, 1H), 7.57–7.53 (m, 2H), 7.51–7.47
(m, 2H), 7.44–7.36 (m, 3H), 6.87 (d, J = 15.6 Hz, 1H); 13C NMR
(CDCl3, 100 MHz) δ 142.4, 140.7, 133.3, 132.3, 131.2, 129.3
(2C), 129.0 (2C), 128.5 (2C), 127.6 (2C), 127.2.
4.2.19. (E)-Naphth-2-ly 2-phenylethenyl sulfone
(5t).
White solid (134 mg, 91%), mp 141–143 °C (lit.[19a] 140–142
oC); H NMR (CDCl3, 400 MHz) δ 8.55 (s, 1H), 8.00–7.97 (m,
1
4.2.12. (E)-Phenyl 2-(4-methylphenyl)ethenyl
sulfone (5m).
2H), 7.92–7.87 (m, 2H), 7.75 (d, J = 15.2 Hz, 1H), 7.68–7.60 (m,
2H), 7.50–7.46 (m, 2H), 7.43–7.35 (m, 3H), 6.92 (d, J = 15.2 Hz,
1H); 13C NMR (CDCl3, 100 MHz) δ 142.5, 137.4, 135.1, 132.3,
132.2, 131.2, 129.6, 129.3, 129.2, 129.1, 129.0 (2C), 128.5 (2C),
127.9, 127.6, 127.2, 122.5.
White solid (120 mg, 93%), mp 119–120 °C (lit.[19b] 118–120
oC); 1H NMR (CDCl3, 400 MHz) δ 7.96–7.94 (m, 2H), 7.66 (d, J
= 15.2 Hz, 1H), 7.63–7.59 (m, 1H), 7.56–7.52 (m, 2H), 7.38 (d, J
= 8.0 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 15.6 Hz,
1H), 2.37 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ 142.5, 141.8,
140.9, 133.2, 129.8 (2C), 129.6, 129.3 (2C), 128.5 (2C), 127.5
(2C), 126.0, 21.5.
4.2.20. (E)-4-Methylphenyl 2-methyl-2-
phenylethenyl sulfone (5u).
White solid (45 mg, 33%), mp 90–91 °C (lit.[19a] 86–88 oC); 1H
NMR (CDCl3, 400 MHz) δ 7.85 (d, J = 8.4 Hz, 2H), 7.40–7.33
(m, 7H), 6.60 (q, J = 1.2 Hz, 1H), 2.52 (d, J = 1.2 Hz, 3H), 2.44
(s, 3H); 13C NMR (CDCl3, 100 MHz) δ 152.9, 144.1, 140.2,
139.3, 129.8 (2C), 129.8, 128.7 (2C), 127.8, 127.2 (2C), 126.3
(2C), 21.6, 17.1.
4.2.13. (E)-Phenyl 2-(4-tert-butylphenyl)ethenyl
sulfone (5n).
White solid (141 mg, 94%), mp 117–119 °C (lit.[19c] 116–118
oC); 1H NMR (CDCl3, 400 MHz) δ 7.96–7.93 (m, 2H), 7.68 (d, J
= 15.2 Hz, 1H), 7.63–7.59 (m, 1H), 7.56–7.52 (m, 2H), 7.44–
7.39 (m, 4H), 6.82 (d, J = 15.2 Hz, 1H), 1.31 (s, 9H); 13C NMR
(CDCl3, 100 MHz) δ 155.0, 142.5, 140.9, 133.2, 129.6, 129.3
(2C), 128.4 (2C), 127.5 (2C), 126.2, 126.0 (2C), 35.0, 31.1 (3C).
4.2.21. (E)-Phenyl 2-methyl-2-phenylethenyl
sulfone (5v).
Yellowish viscous oil[19e] (27 mg, 21%); 1H NMR (CDCl3, 400
MHz) δ 7.99–7.97 (m, 2H), 7.64–7.54 (m, 3H), 7.41–7.33 (m,
5H), 6.61 (q, J = 1.2 Hz, 1H), 2.53 (d, J = 0.8 Hz, 3H); 13C NMR
(CDCl3, 100 MHz) δ 153.5, 142.1, 140.1, 133.2, 129.9, 129.2
(2C), 128.7 (2C), 127.4, 127.2 (2C), 126.3 (2C), 17.2.
4.2.14. (E)-Phenyl 2-(4-chlorophenyl)ethenyl
sulfone (5o).
White solid (118 mg, 85%), mp 128–129 °C (lit.[19b] 128–130
1
oC); H NMR (CDCl3, 400 MHz) δ 7.95 (d, J = 8.4 Hz, 2H),
4.2.22. (E)-4-Fluorophenyl 2-methyl-2-
phenylethenyl sulfone (5w).
7.66–7.62 (m, 2H), 7.56 (t, J = 7.6 Hz, 2H), 7.42 (d, J = 8.8 Hz,
2H), 7.36 (d, J = 8.4 Hz, 2H), 6.85 (d, J = 15.6 Hz, 1H); 13C
NMR (CDCl3, 100 MHz) δ 140.9, 140.4, 137.2, 133.5, 130.8,
129.7 (2C), 129.3 (4C), 127.8, 127.6 (2C).
Yellowish viscous oil (47 mg, 34%); IR v 1590, 1492, 1289
1
cm-1; H NMR (CDCl3, 400 MHz) δ 8.02–7.97 (m, 2H), 7.41–
7.34 (m, 5H), 7.25–7.20 (m, 2H), 6.59 (q, J = 1.2 Hz, 1H), 2.53

6
Tetrahedron
(d, J = 0.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ 165.4 (d,
(d) S. Oishi, K. Hatano, A. Tsubouchi, T. Takeda, Chem. Commun. 47
(2011) 11639–11640.
7. For selected reviews: (a) Y. Fang, Z. Luo, X. Xu, RSC Adv. 6 (2016)
59661–59676;
JCF = 255.0 Hz), 153.7, 139.9, 138.2 (d, JCF = 3.0 Hz), 130.1,
130.0 (2C), 128.7 (2C), 127.2, 126.2 (2C), 116.5 (d, JCF = 23.0
Hz, 2C), 17.1. HRMS (ESI-TOF) (m/z): calcd for C15H14FO2S,
[M+H]+ 277.0693; found 277.0692.
(b) N.-W. Liu, S. Liang, G. Manolikakes, Synthesis 48 (2016) 1939–
1973.
8. (a) C. Najera, B. Baldo, M. Yus, J. Chem. Soc. Perkin Trans I (1988)
1029–1032;
(b) L. K. Liu, Y. Chi, K.-Y. Jen, J. Org. Chem. 45 (1980) 406–410.
9. W. E. Truce, G. C. Wolf, J. Org. Chem. 36 (1971) 1727–1732.
10. (a) L. Wang, H. Yue, D. Yang, H. Cui, M. Zhu, J. Wang, W. Wei, H.
Wang, J. Org. Chem. 82 (2017), 6857−6864;
4.2.23. (E)-4-Nitrophenyl 2-methyl-2-phenylethenyl
sulfone (5x).
White solid (49 mg, 32%), mp 122–123 °C; IR v 1593, 1520,
1
1301 cm-1; H NMR (CDCl3, 400 MHz) δ 8.40 (d, J = 8.8 Hz,
2H), 8.17 (d, J = 8.8 Hz, 2H), 7.44–7.36 (m, 5H), 6.61 (q, J = 1.2
Hz, 1H), 2.56 (d, J = 1.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ
156.1, 150.4, 147.7, 139.5, 130.4, 128.9 (2C), 128.6 (2C), 126.3
(2C), 125.8, 124.5 (2C), 17.4. HRMS (ESI-TOF) (m/z): calcd for
C15H12NO4S, [M-H]- 302.0493; found 302.0493.
(b) R. R. Wolff, V. Basava, R. M. Giuliano, W. J. Boyko, J. H. Schauble,
Can. J. Chem. 84 (2006) 667–675;
11. L. Kadari, R. K. Palakodety, L. P. Yallapragada, Org. Lett. 19 (2017)
2580–2583.
12. (a) Q. Gui, K. Han, Z. Liu, Z. Su, X. He, H. Jiang, B. Tian, Y. Li, Org.
Biomol. Chem. 16 (2018) 5748–5751;
(b) T. Sawangphon, P. Katrun, K. Chaisiwamongkhol, M. Pohmakotr, V.
Reutrakul, T. Jaipetch, D. Soorukram, C. Kuhakarn, Synth. Commun. 43
(2013) 1692–1707;
(c) B. Das, M. Lingaiah, K. Damodar, N. Bhunia, Synthesis (2011)
2941–2944;
4.2.24. (E)-4-Naphthyl 2-methyl-2-phenylethenyl
sulfone (5y).
White solid (39 mg, 25%), mp 92–94 °C; IR v 1596, 1305 cm-
1
1; H NMR (CDCl3, 400 MHz) δ 8.56 (d, J = 1.2 Hz, 1H), 8.01–
(d) N. Taniguchi, Synlett (2011) 1308–1312;
7.98 (m, 2H), 7.94–7.90 (m, 2H), 7.67–7.59 (m, 2H), 7.39–7.31
(m, 5H), 6.68 (q, J = 1.6 Hz, 1H), 2.56 (d, J = 1.6 Hz, 3H); 13C
NMR (CDCl3, 100 MHz) δ 153.6, 140.1, 139.0, 135.0, 132.1,
129.8, 129.6, 129.3, 129.0, 128.7 (2C), 128.5, 127.9, 127.6,
127.4, 126.3 (2C), 122.3, 17.2. HRMS (ESI-TOF) (m/z): calcd
for C19H17O2S, [M+H]+ 309.0944; found 309.0940.
(e) P. Katrun, S. Chiampanichayakul, K. Korworapan, M. Pohmakotr, V.
Reutrakul, T. Jaipetch, C. Kuhakarn, Eur. J. Org. Chem. (2010) 5633–
5641;
(f) V. Nair, A. Augustine, T. Suja, Synthesis (2002) 2259–2265;
(g) V. Nair, A. Augustine, T. G. George, L. G. Nair, Tetrahedron Lett. 42
(2001) 6763–6765;
(h) J. Barluenga, J. M. Martínez-Gallo, C. Nájera, F. J. Fañanás, M. Yus,
J. Chem. Soc., Perkin Trans. 1 (1987) 2605–2609;
(i) K. Inomata, S.-i. Sasaoka, T. Kobayashi, Y. Tanaka, S. Igarashi, T.
Ohtani, H. Kinoshita, H. Kotake, Bull. Chem. Soc. Jpn. 60 (1987) 1767–
1779.
Acknowledgments
This work was supported by National Natural Science
Foundation of China (Nos. 21971138 and 21472107).
13. For selected references of metal-free methods, see: (a) W.-H. Bao, W.-
W. Ying, X.-D. Xu, G.-D. Zhou, X.-X. Meng, W.-T. Wei, Y.-Y. Liu, Q.
Li, Tetrahedron Lett. 60 (2019) 55–58;
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Highlights
1. N,N’-Disulfonylhydrazines were introduced as new sulfonylating reagents.
2. They decomposed efficiently to give sulfonyl radicals promoted by NIS/Et3N.
3. Their combinations with NIS/Et3N were new iodosulfonylating reagents of
alkenes.
4. A new method for highly efficient synthesis of (E)-vinyl sulfones was developed.

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: