Synthesis of (E)-β-iodovinyl sulfones via DTBP/I2 promoted difunctionalization of alkynes with sodium benzenesulfinates

Article abstract of DOI:10.1080/10426507.2016.1259622

The present reaction provides a simple and convenient synthetic strategy to construct β-iodovinyl sulfones through molecular iodine and DTBP (di-tert-butyl peroxide) promoted difunctionalization of alkynes with sodium benzenesulfinates under mild and envi

Full text of DOI:10.1080/10426507.2016.1259622

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis of (E)-β-iodovinyl sulfones via DTBP/
I2 promoted difunctionalization of alkynes with
sodium benzenesulfinates
Wenzhu Bi, Chunyan Ren, Linguo Jia, Xiaoyi Xia, Xi Chen, Xiaolan Chen &
Yufen Zhao
To cite this article: Wenzhu Bi, Chunyan Ren, Linguo Jia, Xiaoyi Xia, Xi Chen, Xiaolan Chen &
Yufen Zhao (2016): Synthesis of (E)-β-iodovinyl sulfones via DTBP/I promoted difunctionalization
2
of alkynes with sodium benzenesulfinates, Phosphorus, Sulfur, and Silicon and the Related
Elements, DOI: 10.1080/10426507.2016.1259622
To link to this article: http://dx.doi.org/10.1080/10426507.2016.1259622
View supplementary material
Accepted author version posted online: 16
Nov 2016.
Published online: 16 Nov 2016.
Submit your article to this journal
Article views: 9
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=gpss20
Download by: [University of Newcastle, Australia]
Date: 10 February 2017, At: 19:15

PHOSPHORUS, SULFUR, AND SILICON
http://dx.doi.org/./..
SHORT COMMUNICATION
Synthesis of (E)-β-iodovinyl sulfones via DTBP/I promoted difunctionalization of

alkynes with sodium benzenesulfinates
a
a
a
a
a
a
a,b
Wenzhu Bi , Chunyan Ren , Linguo Jia , Xiaoyi Xia , Xi Chen , Xiaolan Chen , and Yufen Zhao
a
b
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, China; Department of Chemistry, Xiamen University, Xiamen,
China
ABSTRACT
ARTICLE HISTORY
The present reaction provides a simple and convenient synthetic strategy to construct β-iodovinyl sulfones
through molecular iodine and DTBP (di-tert-butyl peroxide) promoted difunctionalization of alkynes with
sodium benzenesulfinates under mild and environmentally-benign conditions. A series of substituted (E)-
β-iodovinyl sulfones were synthesized with excellent stereo- and regio-selectivities.
Received  September 
Accepted  November 
KEYWORDS
β-Iodovinyl sulfones;
alkynes; sodium
benzenesulfinates; molecular
iodine
GRAPHICAL ABSTRACT
Introduction
methods suffered from some obvious disadvantages such as
the low atom economy, low reaction yields, high reaction
temperature and long reaction time. Meanwhile, the direct
difunctionalization of alkynes with sodium benzenesulfinates
to construct (E)-β-iodovinyl sulfones were also well developed.
Nair et al. reported the synthesis of (E)-β-iodovinyl sulfones
via a cerium(IV) ammonium nitrate (CAN) mediated difunc-
tionalization of alkynes in the presence of NaI (Scheme 2,
eq. (a)).10 Kuhakarn et al. reported a (diacetoxyiodo)benzene
β-Iodovinyl sulfones have drawn great attention from chemists
due to their biological activities and are widely used as building
blocks for various organic transformations in synthetic chem-
istry (Scheme 1).2 Recently, Wnuk et al. reported that β-
iodovinyl sulfones undergo efficient stereoselective nucleophilic
substitution with amines or thiols to provide (Z)-β-aminovinyl
or (E)-β-thiovinyl sulfones tethered to the C5 position of the
1
–4
2
uracil ring (Scheme 1, eq. (1)). Xie et al. reported that (E)-β-
iodovinyl sulfones were used to synthesize sulfonyl-substituted
[PhI(OAc)2, DIB] promoted reaction to afford β-iodovinyl sul-
fones from sodium aryl sulfinate and alkenes under mild reac-
tion conditions (Scheme 2, eq. (b)).11 In 2013, they reported
an improved synthesis of β-iodovinyl sulfones by a molecu-
lar iodine-mediated one-pot reaction in the presence of 1.5
eq. of NaOAc (Scheme 2, eq. (c)).12 Very recently, Taniguchi’s
group demonstrated an aerobic copper-catalyzed synthesis of β-
iodovinyl sulfones via iodosulfonylation of alkynes with aryl sul-
finates (Scheme 2, eq. (d)).13 However, these above mentioned
methods suffer from some obvious drawbacks such as the use of
transition-metal catalyst, stoichiometric amounts of bases, toxic
or potentially dangerous oxidants. Therefore, it is still highly
desired to develop a simple, mild, efficient, atomeconomic and
environmentally-benign method to construct β-iodovinyl sul-
fones. Herein, we report a simple and convenient method to syn-
thesize (E)-β-iodovinyl sulfones through molecular iodine and
DTBP promoted difunctionalization of alkynes with sodium
benzenesulfinates under mild and environmentally-benign con-
ditions (Scheme 2).
1
,3-enynes via Sonogashira coupling reaction with terminal
alkynes and the sulfonyl group could be further transformed
to various substitutents by desulfonylation coupling reactions
3
(
Scheme 1, eq. (2)). Inomata et al. reported the (E)-β-iodovinyl
sulfones could be converted to their corresponding allylic sul-
fones in the presence of 5% Pd-C under hydrogen atmosphere
in methanol or DBU (1,8-diazabicycloundec-7-ene) in CH3CN.
(
Scheme 1, eqs. (3) and (4)).4
From a synthetic standpoint, the most straightforward and
useful strategies to synthesize β-halovinyl sulfones were the
direct difunctionalization of alkynes with sulfonyl halides.5
However, the instability of sulfonyl iodide greatly limited the
6
application of this method to construct β-iodovinyl sulfones.
In recent years, stable sulfone precursor, such as sulfonyl-
7
8
9
hydrazides, benzenesulfonyl chlorides, and sulfinic acids,
were employed for the direct difunctionalization of alkynes to
construct β-iodovinyl sulfones. Unfortunately, these reported
CONTACT Xiaolan Chen
chenxl@zzu.edu.cn
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou , China.
Supplemental data for this article can be accessed on the publisher’s website at http://dx.doi.org/./..
©
 Taylor & Francis Group, LLC

2
W. BI ET AL.
Scheme . Application of some (E)-β-iodovinyl sulfone derivatives.
Scheme . Synthesis of (E)-β-iodovinyl sulfones from alkynes and sodium benzenesulfinates.
Table . Optimization of the reaction conditions.a
Entry
I (eq.)
Ox. (eq.)
Solvent
Temp. (°C)
a (eq.)
Yield (%)b

.
.
.
.
.
.
K S O ()
CH OH-H O



























.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%
%





















K S O ()
CH OH-H O
 
CH OH-H O
 
CH OH-H O
 
CH OH-H O
 
CH OH-H O
 
CH OH-H O
 
CH OH-H O
 



K S O ()



K S O ()



K S O ()



K S O ()



.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
m-CPBA ()
(NH ) S O ()




H O ()
CH OH-H O














TBHP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP ()
DTBP()
DTBP ()
DTBP ()
CH OH-H O
 
CH OH-H O


CH OH-H O
 
CH OH-H O


AcOH-H O

DMF-H O

C H OH-H O



C H OH-H O





C H OH-H O
  
C H OH-H O











C H OH-H O
  
C H OH-H O



C H OH-H O
  
C H OH-H O





C H OH-H O
  
C H OH-H O
  






C H OH-H O



C H OH-H O



a
Reaction conditions: alkyne (. mmol), I (.–. eq.), sodium benzenesulfinates (.–. eq.), solvent ( mL:  mL) at –°C for  h.

bIsolated yields.

PHOSPHORUS, SULFUR, AND SILICON
3
Scheme . Scope of the reaction.a,b
Results and discussion
were used. Then the influence of temperature on the model reac-
tion showed that the yield increased over the temperature range
of 20-60°C (entries 16-20), and then decreased (entries 21-22).
At last, the exploration of the ideal amount of sodium benzene-
sulfinate (2a) showed that 2.0 eq. of 2a gave the highest yield of
We initiated this study by establishing optimal experimental
conditions using the model reaction of phenylacetylene (1a)
with sodium benzenesulfinate (2a) as shown in Table 1. The
amount of iodine employed in the model reaction was first
investigated by reacting 1a with 2a in the presence of K2S2O8
3
a (91%) (entries 20, 23-27). Therefore, the optimized reaction
conditions for the construction of 3a was 1.0 eq. of I2, 2.0 eq. of
DTBP and 2.0 eq. of sodium benzenesulfinate in C2H5OH-H2O
(
2.0 eq.) at 30°C for 2 h (Table 1, entries 1-6). It can be seen that
the yield increased over the amount of iodine range of 0.25 eq. to
.0 eq. (entries 1-4), and then decreased (entries 5-6). The effects
(
v:v = 1:1) at 60°C for 2 h (entry 25).
1
With the optimized raction conditions in hand, the substrate
of some common oxidant reagents on the reaction were then
investigated (entries 4, 7-11). K2S2O8, m-CPBA, (NH4)2S2O8,
H2O2 and TBHP (tert-butyl hydroperoxide) exhibited almost
the same activity for the model reaction (entries 4, 7-10). Only
DTBP (di-tert-butyl peroxide) afforded a moderate yield of 3a
scope of phenylacetylene and sodium benzenesulfinate was then
examined as demonstrated in Scheme 3. As it can be seen, a
variety of sodium benzenesulfinates reacted well with pheny-
lacetylene itself, in addition to sodium methanesulfinate. We
found that the substitute groups on sodium benzenesulfinate did
not affect the yield of the correspongding compounds. Electron
donating groups on phenylacetylene also gave excellent yields;
while the electron withdrawing groups on phenylacetylene
or acetylene significantly decreased the yields of β-iodovinyl
(
49%) (entriy 11). The investigation on the amount of DTBP
entries 11-13) indicated that 2 eq. of oxidant still gives the best
(
yield of 3a. The investigation of solvent system employed on the
model reaction showed a significate increase in the yield of 3a
(49-78%) (entries 11, 14-16) when C2H5OH-H2O (v:v = 1:1)

4
W. BI ET AL.
Scheme . A general pathway for the difunctionalization of alkynes.
sulfones. However, the yields of the corresponding β-iodovinyl organic layer was washed with water and dried over anhydrous
sulfones were relatively low when aliphatic terminal alkynes Na2SO4. The solvent was removed in vacuum and the target
were employed in this reaction and these reaction conditions compound was obtained by column chromatography on silica
were not suitable to convert sodium trifluoromethanesulfinate gel (petroleum ether: ethyl acetate = 15: 1, v: v).
to its β-iodovinyl sulfones derivatives.
Based on the knowledge that sulfonyl radical species are
easily generated from sodium benzenesulfinates under air oxi-
dizing environment,14 a general reaction pathway is proposed
and demonstrated in Scheme 4. Firstly, the sulfonyl radical
1
was generated from sodium benzenesulfinates under DTBP.
(
E)-(1-iodo-2-(phenylsulfonyl)vinyl)benzene (3a) Isolated
Then, the addition of sulfonyl radical to alkyne 2b gave the
alkenyl radical 2, which further interacted with molecular
iodine leading to the formation of the desired β-iodovinyl
sulfone 3a.6
1
Yield 91%. Yellow oil. H NMR (400 MHz, δ-DMSO) δ: 7.17(t,
2
2
6
H, 2-H), 7.33(t, 1H, 4-H), 7.56 (t, 2H, 3-H), 7.65(d, J = 7.6 Hz,
H, 9-H), 7.68 (m, 2H, 8-H), 7.70(m, 1H, 10-H), 7.81(s, 1H,
-H). 13C NMR (400 MHz, δ-DMSO) δ: 116.5(5-C), 127.6(2-
C), 127.8(4-C), 128.4(3-C), 129.8(8-C), 129.9(9-C), 134.3(6-C),
140.2(10-C), 140.67(1-C), 140.71(7-C). HR MS (ESI-Q-TOF):
,10
Conclusion
+
[
M+H] , Cal.: 370.9597, found: 370.9601.
In conclusion, a simple and efficient approach for the synthesis
of (E)-β-iodovinyl sulfones via the molecular iodine promoted
direct difunctionalization of alkynes with sodium benzenesulfi-
nates were developed. The new synthesis methodology provides
an alternative route to various (E)-β-iodovinyl sulfones from
easily available starting materials without transition-metal cata-
lyst or potentially dangerous oxidants.
(
E)-1-chloro-4-((2-iodo-2-phenylvinyl)sulfonyl)benzene
1
(
3b) Isolated Yield 89%. Yellow oil. H NMR (400 MHz, δ-
DMSO) δ: 7.17(t, 2H, 2-H), 7.31(t, 3H, 3, 4-H), 7.56 (d, J =
All the chemicals were obtained from Tianjin Kermel Chemical 13
Experimental section
8
.4 Hz, 2H, 9-H), 7.64(d, J = 8.4 Hz, 2H, 8-H), 7.81(s, 1H, 6-H).
C NMR (400 MHz, δ-DMSO) δ: 116.9(5-C), 127.5(2-C),
28.4(3-C), 129.8(8-C), 129.9(4-C), 133.3(9-C), 139.3(6-C),
Reagent Co., Ltd., and Shanghai Aladdin Bio-Chem Technology
1
1
13
Co., Ltd., and used as received. H, and C NMR spectra were
recorded with a Bruker Avance 400 MHz spectrometer oper-
ating at 400.13 and 100.61 MHz, respectively, with 13C NMR
spectra being recorded with broad band proton decoupled. All
NMR spectra were recorded in δ-DMSO at room temperature
1
39.5(10-C), 139.9(1-C), 140.6(7-C). HR MS (ESI-Q-TOF):
+
[
M+H] , Cal.: 404.9207, found: 404.9211.
1
13
(
20 ± 3°C). H and C chemical shifts are quoted in parts
per million downfield from TMS. High resolution mass spectra
HR MS) were obtained with a Waters Micromass Q-Tof Micro
instrument using the ESI technique. The Supplemental Materi-
(
(
E)-1-((2-iodo-2-phenylvinyl)sulfonyl)-4-methylbenzene
1
13
als contains sample H and C NMR spectra for the products 3
Figures S1–S30).
1
(
3c) Isolated Yield 94%. Yellow oil. H NMR (400 MHz, δ-
(
DMSO) δ: 2.35(s, 3H, 11-H), 7.17(dd, J = 2.0 Hz, J = 5.6 Hz,
2
H, 3-H), 7.32-7.34(m, 5H, 2, 4, 9-H), 7.53(d, J = 8.4 Hz,
13
General procedure
2H, 8-H), 7.74(s, 1H, 6-H). C NMR (400 MHz, δ-DMSO)
δ: 21.6(11-C), 115.9(5-C), 127.6(2-C), 127.9(3-C), 128.3(8-C),
Synthesis of (E)-β-iodovinyl sulfones
129.8(4-C), 130.4(9-C), 137.8(6-C), 140.4(10-C), 140.7(1-C),
+
1
44.9(7-C). HR MS (ESI-Q-TOF): [M+H] , Cal.: 384.9754,
I2 (0.5 mmol) was added to a solution of alkynes (0.5 mmol),
sodium benzenesulfinates (1.0 mmol) and DTBP (1.0 mmol)
in C2H5OH: H2O (2 mL:2 mL), and the reaction mixture was
stirred and heated at 60°C for 2.0 h. Then, the mixture was
cooled to room temperature, quenched by Na2S2O3, diluted
with water and extracted by CH2Cl2 (10 mL × 3). The combined
found: 384.9759.

PHOSPHORUS, SULFUR, AND SILICON
5
(
E)-(1-iodo-2-(methylsulfonyl)vinyl)benzene (3d) Isolated 7.67(t, 2H, 7-H), 7.74-7.78(m, 1H, 8-H), 7.95(d, J = 6.4 Hz,
1 13
Yield 73%. Yellow oil. H NMR (400 MHz, δ-DMSO) δ: 2H, 6-H). C NMR (400 MHz, δ-DMSO) δ: 12.0(2-C), 17.4(1-
.95(s, 3H, 7-H), 7.36-7.37(m, 5H, 2, 3, 4-H) 7.71(s, 1H, 6- C), 127.4(6-C), 130.2(7-C), 134.3(4-C), 135.5(3-C), 137.6(8-C),
2
13
+
H). C NMR (400 MHz, δ-DMSO) δ: 43.5(7-C), 114.9(5- 141.5(5-C). HR MS (ESI-Q-TOF): [M+H] , Cal.: 334.9597,
C), 128.0(2-C), 128.4(3-C), 130.0(4-C), 140.0(6-C), 140.8(1-C). found: 334.9599.
+
HR MS (ESI-Q-TOF): [M+H] , Cal.: 308.9441, found: 308.
9
441.
(
E)-((2-cyclohexyl-2-iodovinyl)sulfonyl)benzene (3i) Iso-
1
lated Yield 53%. Yellow oil. H NMR (400 MHz, δ-DMSO) δ:
(
E)-1-(1-iodo-2-(phenylsulfonyl)vinyl)-4-methylbenzene
1
8
2
.04-1.71(m, 10H, 2, 3, 4, 5, 6-H), 2.78(m, 1H, 1-H), 7.44 (s, 1H,
1
(
3e) Isolated Yield 85%. Yellow oil. H NMR (400 MHz,
-H), 7.69(t, 2H, 11-H), 7.77(t, 1H, 12-H), 7.94(d, J = 7.2 Hz,
δ-DMSO) δ: 2.30(s, 3H, 11-H), 7.08-7.14(m, 4H, 2, 3-H),
13
H, 10-H). C NMR (400 MHz, δ-DMSO) δ: 24.8 (3-C), 25.4(4-
7
1
1
1
.52-7.56(m, 2H, 9-H), 7.65-7.72 (m, 3H, 8, 10-H), 7.75 (s,
H, 6-H). 13C NMR (400 MHz, δ-DMSO) δ: 21.4(11-C),
16.8(5-C), 127.7(2-C), 127.8(4-C), 128.9(3-C), 129.8(8-C),
C), 33.2(2-C), 43.2(1-C), 127.6(7-C), 130.3(11-C), 134.5(12-C),
1
[
37.0(8-C), 138.3(13-C), 141.5(10-C). HR MS (ESI-Q-TOF):
+
M+H] , Cal.: 377.0067, found: 377.0071.
34.2(9-C), 137.8(6-C), 139.7(10-C), 139.9(1-C), 140.7(7-C).
+
HR MS (ESI-Q-TOF): [M+H] , Cal.: 384.9754, found: 384.
9759.
(
E)-methyl 2-iodo-3-(phenylsulfonyl)acrylate (3j) Isolated
1
Yield 33%. Yellow oil. H NMR (400 MHz, δ-DMSO) δ: 3.84(s,
3
H, 1-H), 7.71(t, 2H, 7-H), 7.79-7.81 (m, 2H, 4, 8-H), 7.88
(
E)-1-bromo-4-(1-iodo-2-(phenylsulfonyl)vinyl)benzene
13
1
(d, J = 7.6 Hz, 2H, 6-H). C NMR (400 MHz, δ-DMSO)
(
3f) Isolated Yield 89%. Yellow oil. H NMR (400 MHz, δ-
δ: 53.9(1-C), 103.7(3-C), 128.0(6-C), 130.3(7-C), 135.0(8-C),
DMSO) δ: 7.15(d, J = 8.4 Hz, 2H, 2-H), 7.54-7.59(m, 4H, 3,
-H), 7.68-7.73 (m, 3H, 8, 10-H) 7.83(s, 1H, 6-H). 1 C NMR
3
139.2(5-C), 139.3(4-C), 166.4(2-C). HR MS (ESI-Q-TOF):
9
+
[
M+H] , Cal.: 352.9339, found: 352.9343.
(
400 MHz, δ-DMSO) δ: 114.6(5-C), 123.2(2-C), 127.9(4-C),
1
1
4
29.6(3-C), 130.0(8-C), 131.4(9-C), 134.4(6-C), 140.1(10-C),
+
40.4(1-C), 140.7(7-C). HR MS (ESI-Q-TOF): [M+H] , Cal.:
48.8702, found: 448.8707.
(
E)-1-bromo-4-(2-((4-chlorophenyl)sulfonyl)-1-
1
iodovinyl)benzene (3k) Isolated Yield 83%. Yellow oil. H
NMR (400 MHz, δ-DMSO) δ: 7.12(d, J = 8.4 Hz, 2H, 2-H),
(
E)-1-fluoro-3-(1-iodo-2-(phenylsulfonyl)vinyl)benzene
7
1
1
1
.54(d, J = 7.6 Hz, 2H, 3-H), 7.62-7.69 (m, 4H, 7, 8-H), 7.84(s,
H, 6-H). 13C NMR (400 MHz, δ-DMSO) δ: 119.9(5-C),
28.0(4-C), 134.2(2-C), 134.6(3-C), 134.9(8-C), 136.2(9-C),
1
(
3g) Isolated Yield 43%. Yellow oil. H NMR (400 MHz,
δ-DMSO) δ: 6.99(t, 2H, 2, 2’-H), 7.15-7.20(m, 1H, 4-H),
7
.37-7.42 (m, 1H, 3’-H), 7.58(t, 2H, 9-H), 7.67(d, J = 7.6 Hz,
43.9(6-C), 144.3(10-C), 144.76(1-C), 140.78(7-C). HR MS
ESI-Q-TOF): [M+H] , Cal.: 482.8313, found: 482.8313.
2
H, 8-H), 7.72(t, 1H, 10-H), 7.84(s, 1H, 6-H). 13C NMR
+
(
(
400 MHz, δ-DMSO) δ: 114.0(5-C), 114.3(J = 22.3 Hz, 2-C),
1
1
1
16.5(J = 20.4 Hz, 4-C), 123.6(J = 2.7 Hz, 2’-C), 127.8(8-C),
30.0 (9-C), 130.5(J = 8.4 Hz, 3’-C), 134.4(6-C), 140.4(10-C),
40.7(7-C), 142.8(J = 6.8 Hz, 1-C), 140.2(J = 243.4 Hz, 3-C).
+
HR MS (ESI-Q-TOF): [M+H] , Cal.: 388.9503, found: 388.
9
507.
(
E)-1-chloro-4-((2-cyclohexyl-2-iodovinyl)sulfonyl)
1
benzene (3l) Isolated Yield 43%. Yellow oil. H NMR (400 MHz,
δ-DMSO) δ: 1.04-1.72(m, 10H, 2, 3, 4, 5, 6-H), 2.78(m, 1H,
1
-H), 7.45 (s, 1H, 8-H), 7.76(d, J = 8.8 Hz, 2H, 10-H), 7.95(d,
13
J = 7.2 Hz, 2H, 11-H). C NMR (400 MHz, δ-DMSO) δ: 24.8
(
E)-((2-cyclopropyl-2-iodovinyl)sulfonyl)benzene (3h) Is- (3-C), 25.4(4-C), 33.3(2-C), 43.3(1-C), 129.6(7-C), 130.4(11-
1
olated Yield 63%. Yellow oil. H NMR (400 MHz, δ-DMSO) C), 137.5(12-C), 137.8(8-C), 139.6(13-C), 140.2(10-C). HR MS
+
δ: 0.71-0.94(m, 4H, 2-H), 2.37(m, 1H, 1-H), 7.42 (s, 1H, 4-H), (ESI-Q-TOF): [M+H] , Cal.: 410.9677, found: 410.9677.

6
W. BI ET AL.
Funding
The authors acknowledge financial support from 2015 Graduate Innovation
Projects in Zhengzhou University (No. FMCZ002).
References
(
E)-1-chloro-4-((2-iodo-2-(p-tolyl)vinyl)sulfonyl)benzene
1
. (a) Palmer, J. T.; Rasnick, D.; Klaus, J. L.; Bromme, D. J. Med. Chem.
1
(
3m) Isolated Yield 53%. Yellow oil. H NMR (400 MHz, δ-
1
995, 38, 3193-3196; (b) Meadows, D. C.; Gervay-Hague, J. Med. Res.
DMSO) δ: 2.32(s, 3H, 11-H), 7.06(d, J = 8.4 Hz, 2H, 2-H),
Rev. 2006, 26, 793-814; (c) Ettari, R.; Nizi, E.; Francesco, M. E. D.;
Dude, M. A.; Pradel, G.; Vicik, R.; Schirmeister, T.; Micale, N.; Grasso,
S.; Zappala, M. J. Med. Chem. 2008, 51, 988-996.
. Liang, Y.; Suzol, S. H.; Wen, Z. W.; Artiles, A. G.; Mathivathanan, L.;
Raptis, R. G.; Wnuk, S. F. Org. Lett. 2016, 18, 1418-1421.
. Gu, X. X.; Xie, M. H.; Zhao, X. Y.; Sun, Y.; Zhang, W.; Xie, F. D.; Wang,
S. W. Chin. J. Chem. 2008, 26, 1625-1629.
7
1
1
1
.13 (d, J = 8.0 Hz, 2H, 3-H), 7.60-7.65(m, 4H, 8, 9-H), 7.77(s,
H, 6-H). 13C NMR (400 MHz, δ-DMSO) δ: 21.4(11-C),
17.3(5-C), 127.6(2-C), 128.9(3-C), 129.8(8-C), 130.0(9-C),
2
37.8(4-C), 139.3(6-C), 139.4(10-C), 139.5(1-C), 139.8(7-C).
3
+
HR MS (ESI-Q-TOF): [M+H] , Cal.: 418.9364, found: 418.
9
368.
4. (a) Kobayashi, T.; Tanaka, Y.; Ohtani, T.; Kinoshita, H.; Inomata, K.;
Kotake, H. Chem. Lett. 1987, 16, 1209-1212; (b) Hu, F.; Gao, W. C.;
Chang, H. H.; Li, X.; Wei, W. L. Chin. J. Org. Chem. 2015, 35, 1848-
1
860.
5
. (a) Mataunoto, H.; Nakano, T.; Ohkawa K.; Nagai, Y. Chem. Lett. 1978,
3
6
2
63-366; (b) Huang, X.; Duan, D. H.; Zheng, W. X. J. Org. Chem. 2003,
8, 1958-1963; (c) Dubbaka, S. R.; Vogel, P. Chem. Eur. J. 2005, 11,
633-2641; (d) Liu, X. Y.; Duan, X. H.; Pan, Z. L.; Han, Y.; Liang, Y. M.
Synlett. 2005, 11, 1752-1754; (e) Zeng, X.; Ilies, L.; Nakamura, E. Org.
Lett. 2012, 14, 954-956; (f) Wille, U. Chem. Rev. 2013, 113, 813-853;
(
E)-1-(1-iodo-2-(methylsulfonyl)vinyl)-4-methylbenzene
1
(
3n) Isolated Yield 91%. Yellow oil. H NMR (400 MHz, δ-
(
g) Li, X.; Shi, X.; Fang, M.; Xu, X. J. Org. Chem. 2013, 78, 9499-9504.
DMSO) δ: 2.32(s, 3H, 8-H), 2.94(s, 3H, 7-H), 7.19(d, J = 8.0 Hz,
6. (a) Truce, W. E.; Wolf, G. C. J. Org. Chem. 1971, 36, 1727-1732; (b)
Truce, W. E.; Heuring, D. L.; Wolf, G. C. J. Org. Chem. 1974, 39, 238-
13
2
H, 2-H), 7.28(d, J = 7.6 Hz, 2H, 3-H), 7.66(s, 1H, 6-H).
C
2
44.
. (a) Li, X. Q.; Xu, X. S.; Shi, X. H. Tetrahedron Lett. 2013, 54, 3071-3074;
b) Wan, J. P.; Hu, D. Q.; Bai, F. C.; Wei, L.; Liu, Y. Y. RSC Adv. 2016, 6,
3132-73135.
8. Wang, D. Y.; Zhang, R. X.; Lin, S.; Yan, Z. H.; Guo, S. M. Synlett. 2016,
7, 2003-2008.
NMR (400 MHz, δ-DMSO) δ: 21.3(8-C), 43.4(7-C), 115.2(5-C),
7
1
28.2(2-C), 128.9(3-C), 137.9(6-C), 139.6(1-C), 139.9(4-C).
(
7
+
HR MS (ESI-Q-TOF): [M+H] , Cal.: 322.9597, found: 322.
9
599.
2
9
. Wei, W.; Wen, J. W.; Yang, D. S.; Jing, H. J.; You, J. M.; Wang, H. RSC
Adv. 2015, 5, 4416-4419.
1
0. Nair, V.; Augustine, A.; Suja, T. D. Synthesis, 2002, 2259-2265.
1. Katrun, P.; Chiampanichayakul, S.; Korworapan, K.; Pohmakotr, M.;
Reutrakul, V.; Jaipetch, T.; Kuhakarn, C. Eur. J. Org. Chem. 2010, 29,
1
5
633-5641.
1
2. Sawangphon, T.; Katrun, P.; Chaisiwamongkhol, K.; Pohmakotr, M.;
Reutrakul, V.; Jaipetch, T.; Soorukram, D.; Kuhakarn, C. Synth. Com-
mun. 2013, 43, 1692-1707.
(
E)-1-bromo-4-(1-iodo-2-(methylsulfonyl)vinyl)benzene
1
(
3o) Isolated Yield 87%. Yellow oil. H NMR (400 MHz, δ-
DMSO) δ: 3.40(s, 3H, 7-H), 7.31(d, J = 8.4 Hz, 2H, 2-H),
13. Taniguchi, N. Tetrahedron. 2014, 70, 1984-1990.
4. (a) Cui, Z.; Shang, X.; Shao, X. F.; Liu, Z. Q. Chem. Sci. 2012, 3, 2853-
858; (b) Zhang, X.; Wang, L. Green Chem. 2012, 14, 2141-2145. (c) Lu,
13
1
7
(
.58(d, J = 8.4 Hz, 2H, 3-H), 7.75(s, 1H, 6-H). C NMR
2
400 MHz, δ-DMSO) δ: 43.5(7-C), 113.1(5-C), 123.2(6-
Q.; Zhang, J.; Wei, F.; Qi, Y.; Wang, H.; Liu, Z.; Lei, A. W. Angew. Chem.
Int. Ed. 2013, 52, 7156-7159; (d) Wei, W.; Wen, J.; Yang, D.; Du, J.; You,
J.; Wang, H. Green Chem. 2014, 16, 2988-2991; (e) Shen, T.; Yuan, Y.;
Song, S.; Jiao, N. Chem. Commun. 2014, 50, 4115-4118.
C), 130.0(2-C), 131.4(3-C), 140.1(1-C), 140.3(4-C). HR
+
MS (ESI-Q-TOF): [M+H] , Cal.: 386.8546, found: 386.
8
549.