Iodine-promoted decarboxylative C-S cross-coupling of cinnamic acids with sodium benzene sulfinates

Article abstract of DOI:10.1016/j.tet.2015.05.115

We have developed a practical example of metal-free iodine-promoted decarboxyltive couplings between cinnamic acids and sodium benzene sulfinates, which represents an effective synthesis of vinyl sulfones via C-S bond formation reaction.

Full text of DOI:10.1016/j.tet.2015.05.115

Accepted Manuscript
Iodine-Promoted Decarboxylative C−S Cross-Coupling of Cinnamic Acids with
Sodium Benzene Sulfinates
Jie Chen, Jincheng Mao, Yang Zheng, Defu Liu, Guangwei Rong, Hong Yan, Cheng
Zhang, Daqing Shi
PII:
S0040-4020(15)00837-6
10.1016/j.tet.2015.05.115
TET 26834
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 February 2015
Revised Date: 26 May 2015
Accepted Date: 29 May 2015
Please cite this article as: Chen J, Mao J, Zheng Y, Liu D, Rong G, Yan H, Zhang C, Shi D, Iodine-
Promoted Decarboxylative C−S Cross-Coupling of Cinnamic Acids with Sodium Benzene Sulfinates,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.05.115.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
Iodine-Promoted Decarboxylative C−S Cross-Coupling
of Cinnamic Acids with Sodium Benzene Sulfinates
Leave this area blank for abstract info.
Jie Chena, Jincheng Mao,a,b,*Yang Zhenga, Defu Liua, Guangwei Ronga, Hong Yan,a Cheng Zhang,a Daqing
Shia,*
aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Suzhou 215123, P. R. China
b State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum
University, Chengdu, 610500, P. R. China
O
S
I2, TBHP
O
S
COOH
+
R1
R2
R1
toluene, 90 oC, 12 h
O
R2
ONa

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Iodine-Promoted Decarboxylative C−S Cross-Coupling of Cinnamic Acids with
Sodium Benzene Sulfinates
Jie Chena, Jincheng Mao,a,b, * Yang Zhenga, Defu Liua, Guangwei Ronga, Hong Yan,a Cheng Zhang,a
Daqing Shia,*
aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou
215123, P. R. China
bState Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, P. R. China
ARTICLE INFO
ABSTRACT
cle history:
Received
Received in revised form
Accepted
Available online
We have developed a practical example of metal-free iodine-promoted decarboxyltive couplings
between cinnamic acids and sodium benzene sulfinates, which represents an effective synthesis
of vinyl sulfones via C–S bond formation reaction.
2009 Elsevier Ltd. All rights reserved
.
Keywords:
decarboxylative coupling
cinnamic acids
cross-couplings
sulfinates
metal-free
*
Corresponding author. Fax: +86 512 65880403
E-mail address: jcmao@suda.edu.cn (J. Mao); dqshi@suda.edu.cn (D. Shi)

2
8
9
10
2
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.1)
I2 (0.4)
I2 (0.5)
I2 (0.6)
I2 (1.0)
I2 (1.5)
I2 (2.0)
I2 (2.0)
I2 (2.0)
I2 (2.0)
I2 (2.0)
AcOH
THF
ND
Trace
19
13
11
9
18
27
40
48
53
59
82
86
81
92
88
89
1. Introduction
ACCEPTED MANUSCRIPT
2
2
2
2
2
2
4
4
4
4
4
4
4
4
4
4
4
Toluene
ethanol
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
It is well known that vinyl sulfones are valuable building
blocks which are popular as Michael acceptors1 and most of them
usually show a wide range of medicinal activities2. Thus, the
development of efficient synthetic methods about vinyl sulfones
gains great attention. In the past several years, many methods for
the synthesis of vinyl sulfones focused on palladium- or
copper-catalyzed sulfonylation of alkynes3, olefins4, vinyl
halides5, alkenyl boronic acids6, vinyl tosylates7 or epoxides8.
Although great efforts have been made, we thought it would be
interesting to synthesize vinyl sulfones through some straight
ways.
11
12c
13d
14e
15
16
17
18
19
20
21
22f
23g
24h
25i
a
Reaction conditions: 1a (0.3 mmol), 2a (0.6-1.2 mmol), additive (0.1-2
equiv), TBHP in H2O (0.6 mmol), toluene (2 mL), 80 °C, air, 12 h. b Isolated
yield based on 1a. c DTBP. d DCP. e TBHP in decane. f 70 oC;g 90 oC; h 100 oC.
i 1a (1 g), 2a (4 equiv), I2 (2 equiv), TBHP in H2O (2 equiv), toluene (45 mL),
90 °C, air, 12 h.
The screening of various reaction conditions for the
synthesis of (E)-vinyl sulfones is listed in Table 1. First, the
reaction of cinnamic acid 1a (0.3 mmol) with sodium benzene
sulfinate 2a (0.6 mmol) was performed tert-butyl hydroperoxide
(TBHP) (0.6 mmol) as an oxidant in acetonitrile (2 mL) at 80 °C
for 12 h, affording the desired product 3a in 4% yield (Table 1,
entry 1). Considering the poor solubility of sodium benzene
sulfinate in organic solvent, we added phase transfer catalysts
into the system, such as TBAB and TBAI (Table 1, entries
2-3). The use of TBAI led to enhanced yield (8%, Table 1, entry
3). Then we tried other iodine reagents including KI, NaI, I2 and
PhI(OAc)2 (Table 1, entries 4−7). Among them, iodine proved to
be the most effective and led to an increase in the yield to 11%
(Table 1, entry 6). Then, various solvents were tested for this
transformation (Table 1, entries 8−11), and toluene was found to
be the best (Table 1, entry 10). Then, we explored other oxidants,
including di-tert-butyl peroxide (DTBP), dicumyl peroxide
(DCP), and TBHP (in decane) (Table 1, entries 12−14). The
results revealed that they were less effective than TBHP in water
(Table 1, entry 10). Notably, increasing the amount of sodium
sulfinate from 2 to 4 equiv improved the yield of 3a to 27%
(Table 1, entry 15). We believed that in this case sodium benzene
sulfinate worked not only as the substrate but also as the base.
Furthermore, higher loading of iodine resulted in the higher yield
of 3a (Table 1, entries 16−21). The satisfactory yield was
obtained when 2 equiv of iodine was employed (86% yield,
Table 1, entry 21). Through further exploration of the reaction
conditions (Table 1, entries 22−24), it was found that the yield
could be improved to 92% when the reaction temperature was
90 °C (Table 1, entry 23). Under the optimal conditions, the
reaction was performed in gram scale. It can be seen the good
result could be obtained (89% yield, entry 25, Table 1).
Scheme 1. Decarboxylative C–S Cross-Couplings.
Recently, metal-catalyzed decarboxylative cross-couplings of
carboxylic acids have emerged as effective and reliable tools for
the formation of C–C9, C–N10 and C–P11. Also, many methods
have been developed for decarboxylative C–S bond formation
(Scheme 1a-1d)12-15, but the use of metal-catalysts (i.e., Pd, Ag
and Cu) was not friendly to the environment. In addition, few
attention has been paid on decarboxylative C–S bond formation
through sulfonylation of cinnamic acid (Scheme 1e). 16 During
the process of preparation of this manuscript, palladium-, silver-
or copper-catalyzed decarboxylative coupling between sodium
sulfinates and cinnamic acids have been reported by several
groups.16a-16d However, the problem of the potential metal
contamination will limit their massive applications in big-scale
synthesis, especially in the pharmaceutical industry, where needs
serious monitoring of the metal contamination in the products.
Herein, as a continuation of the research on decarboxylative
cross-coupling of cinnamic acids,17 we will develop an
iodine-promoted decarboxylative C–S bond formation through
cinnamic acids and sodium benzene sulfinates in the absence of
metal catalyst.
2. Results and discussion
Table 1. Optimization of the Reaction Conditions a
O
S
O
S
Additive
TBHP
COOH
+
ONa
O
Solvent
1a
2a
3a
Table 2. Substrate Scope for Iodine-Mediated Decarboxylation of Cinnamic
Acids with Sodium Benzene Sulfinatesa
2a
(equiv)
Yield
(%)b
4
ND
8
ND
6
11
entry
Additive (equiv)
Solvent
O
1
2
3
4
5
6
7
2
2
2
2
2
2
2
–
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
O
S
I2, TBHP
S
TBAB (0.1)
TBAI(0.1)
KI (0.1)
COOH
+
R1
R2
R1
toluene, 90oC, 12h
O
R2
ONa
1
2
3
NaI (0.1)
I2 (0.1)
PhI(OAc)2 (0.1)
ND

3
O
S
O
S
O
can also be employed in the reaction to give the desired
ACCEPTED MANUSCRIPT
S
MeO
O
O
products (3n, 3o) in 84% and 92% yield, respectively. Next, we
began to explore the scope of sodium benzene sulfinates partners.
To our delight, no matter whether the electron-rich or -neutral
sodium benzene sulfinates, the reaction proceeded smoothly (3p,
3q, 3w). Functional groups such as Cl and Br could be tolerated,
which gave the good yields in 83% and 86% (3s, 3t). Sodium
benzene sulfinates with NO2 and CF3 group could not react very
well, and only 66% and 74% yields were obtained (3r, 3v).
Encouragingly, 2-naphthalene sulfinic acid sodium salt
successfully coupled with cinnamic acid to afford a good result
(3u).
O
O
O
3a: 92%
3b: 70%
3c: 69%
O
O
S
O
S
MeO
MeO
S
MeO
MeO
O
O
O
MeO
OMe
3f: 40%
3d: 84%
3e: 78%
3h: 55%
O
O
S
O
S
S
O
O
O
O2N
F
3g: 91%
3i: 67%
O
O
O
S
S
S
O
O
O
When cinnamic acid was replaced by styrene under the
standard conditions, 90% yield of desired product could be
acquired (Table 2, 3a). Besides, styrenes with electron donating
group (CH3) and electron withdrawing group (Cl) were suitable
substrates for this transformation with the yields up to 90%
(Table 2, 3i and 3k).
F3C
Cl
3j: 51%
3k
: 68%
3l
: 91%
O
S
O
S
O
S
O
O
O
S
3m: 93%
3n: 92%
3o: 84%
O
S
O
S
O
S
O
O
O
OMe
NO2
3p: 88%
3q: 90%
3r
: 66%
O
S
O
S
O
S
O
O
O
Cl
Br
3s: 86%
3t: 83%
3u: 92%
O
S
O
S
MeO
O
O
CF3
OMe
3w: 72%
3v: 74%
a Reaction conditions: 1 (0.3 mmol), 2 (1.2 mmol), I2 (2 equiv), TBHP in H2O
(0.6 mmol), toluene (2 mL), 90 °C, air, 12 h; Isolated yield based on 1.
Scheme 2. Control Experiments.
To clarify the reaction mechanism, control experiments were
carried out under the standard conditions as shown in Scheme 2.
Trace of 3a was obtained when sodium cinnamate was subjected
to the standard reaction conditions (Scheme 2a). Moreover, only
cinnamic acid was placed under the standard reaction conditions
in the absence of sodium benzene sulfinate, and we could not
detect styrene for 12 hours by GC-MS, which supports the
possibility for the lack of the participation of styrene (Scheme
2b). When the reaction between cinnamic acid and sodium
benzene sulfinate in the presence of TEMPO was conducted
under the standard conditions, only trace of 3a was observed
(Scheme 2c). This suggested that the reaction probably
underwent a radical pathway.
Table 3. Reaction of Alkenes with Sodium Benzene Sulfinatea
a Reaction conditions: Alkene (0.3 mmol), 2a (1.2 mmol), I2 (2 equiv), TBHP
in H2O (0.6 mmol), toluene (2 mL), 90 °C, air, 12 h; Isolated yield based on
alkene.
With the optimized conditions in hand, we began to evaluate
the scope of this reaction with different substituted cinnamic
acids and sodium benzene sulfinates. As demonstrated in Table 2,
it was found that electron-rich, -neutral, and -poor cinnamic acids
could successfully decarboxylative sulfonylation to give the
desired products in modest to excellent yields. For instance,
cinnamic acids with alkoxyl groups gave the corresponding
products in 40−80% yield (3b-3f). Notably, more methoxyl
groups on the aromatic ring from cinnamic acids will lead to
lower yield of 3. Unfortunately, in the reaction of
electron-deficient cinnamic acids, such as NO2, F, CF3, Cl groups,
the expected products was obtained only in 51−68% yield
(3h-3k). In addition, electron-neutral cinnamic acids under the
standard conditions afforded the desired vinyl sulfones in high
yields (3g, 3l, 3m). Furthermore, naphthalenes and thiophenes
Scheme 3. The Plausible Mechanism

4
3H), 6.88 (d, J = 15.2 Hz, 1H), 6.96−7.01 (m, 2H), 7.09 (d, J =
ACCEPTED MANUSCRIPT
According to the above results and pioneering works,[18] the
mechanism for the reaction of cinnamic acid with sodium
benzene sulfinate was proposed as shown in Scheme 3. In the
presence of TBHP the sodium benzene sulfinate will be oxidized
to generate the oxygen-centered radical. Then the
oxygen-centered radical with cinnamic acid can generate an
intermediate A, which then combines with molecular iodine to
form the intermediate B and an iodide radical. B then goes
through decarboxylation and elimination to get the desired
product 3a, HI and CO2. Further, HI is reoxidized to iodide
radical by TBHP, and molecular iodine is generated from two
iodide radicals to complete the cycle.
7.6 Hz, 1H), 7.30 (t, J = 7.8 Hz, 1H), 7.54 (t, J = 7.6 Hz, 2H),
7.61 (d, J = 7.2 Hz, 1H), 7.65 (d, J = 15.6 Hz, 1H), 7.94−7.96 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 55.4, 113.4, 117.2, 121.2,
127.6, 127.7, 129.4, 130.1, 133.4, 133.7, 140.7, 142.5, 160.0;
LRMS: m/z calcd for C15H14O3S (M + H): 275.1, found: 275.1
(E)-5-(2-(phenylsulfonyl)vinyl)benzo[d][1,3]dioxole (3c). Pale
yellow liquid. H NMR (400 MHz, CDCl3) δ 6.01 (s, 6H), 6.69
1
(d, J = 15.2 Hz, 1H), 6.82 (d, J = 8.1 Hz, 1H), 6.95 (d, J = 1.6
Hz, 1H), 6.99−7.02 (dd, J = 1.6, 8.0 Hz, 1H ), 7.53−7.64 (m, 4H),
7.93−7.95 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 101.8, 106.8,
108.7, 125.0, 125.4, 126.6, 127.5, 129.3, 133.3, 141.0, 142.3,
148.5, 150.4; LRMS: m/z calcd for C15H12O4S (M + H): 289.0,
found: 289.0.
3. Conclusions
(E)-1-methoxy-4-(2-(phenylsulfonyl)vinyl)benzene (3d). White
solid, mp = 108 − 110 °C. 1H NMR (400 MHz, CDCl3) δ 3.82 (s,
3H), 6.74 (d, J = 15.6 Hz, 1H), 6.90 (d, J = 8.4 Hz, 2H), 7.44 (d,
J = 8.8 Hz, 2H), 7.52−7.60 (m, 3H), 7.64 (d, J = 15.2 Hz, 1H),
7.95 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 55.5,
114.5, 124.4, 125.0, 127.5, 129.3, 130.4, 133.2, 141.1, 142.3,
162.1; LRMS: m/z calcd for C15H14O3S (M + H): 275.1, found:
275.0.
In conclusion, we have demonstrated an efficient system for
decarbonylative C−S cross-coupling reaction of readily available
cinnamic acids with sodium benzene sulfinates. Low-cost iodine
together with TBHP could promote such decarboxylative
reactions to prepare various useful vinyl sulfones, which
represents a practical method. This metal-free protocol will
probably be applied in the synthesis of some pharmaceutical
intermediates in some cases. The further study on
decarboxylation of other acids and its application is underway in
our laboratory.
(E)-1,2-dimethoxy-4-(2-(phenylsulfonyl)vinyl)benzene
(3e).
1
White solid, mp = 153 − 154 °C. H NMR (400 MHz, CDCl3) δ
3.87 (s, 3H), 3.89 (s, 3H), 6.77 (d, J = 15.6 Hz, 1H), 6.86 (d, J =
8.4 Hz, 1H), 6.99 (d, J = 2.0 Hz, 1H), 7.09 (dd, J = 8.4, 2.0 Hz,
1H), 7.51−7.64 (m, 4H), 7.93−7.96 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 55.9, 56.0, 110.0, 111.1, 123.6, 124.7, 125.2,
127.5, 129.3, 133.2, 141.1, 142.6, 149.3, 151.9; LRMS: m/z
calcd for C16H16O4S (M + H): 305.1, found: 305.1.
4. Experiment
4.1 General information
All reactions were carried out under air. Solvents were dried
and degassed by standard methods. Flash column
chromatography was performed using silica gel (300-400 mesh).
Analytical thin-layer chromatography was performed using glass
plates pre-coated with 200-400 mesh silica gel impregnated with
a fluorescent indicator (254 nm). NMR spectra were measured in
CDCl3 on a Varian Inova-400 NMR spectrometer (400 MHz or
300 MHz) with TMS as an internal reference. Products were
characterized by comparison of 1H NMR, 13C NMR and MS data
in the literature.
(E)-1,2,3-trimethoxy-5-(2-(phenylsulfonyl)vinyl)benzene (3f).
1
Pale yellow solid, mp = 165 − 167 °C. H NMR (400 MHz,
CDCl3) δ 3.85 (s, 6H), 3.85 (s, 3H), 6.73 (s, 2H), 6.84 (d, J =
15.2 Hz, 1H), 7.52−7.63 (m, 4H), 7.93−7.95 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 56.2, 61.0, 105.9, 126.4, 127.6, 127.8, 129.4,
133.4, 140.8, 142.6, 153.5; LRMS: m/z calcd for C17H18O5S (M +
H): 335.1, found: 335.1.
4.2 General Procedure for preparation of iodine-mediated
decarboxylation between cinnamic acid and sodium benzene
sulfinate:
(E)-1-methyl-3-(2-(phenylsulfonyl)vinyl)benzene (3g). Pale
1
A 25 mL tube was charged with cinnamic acid (0.3 mmol),
sodium benzene sulfinate (1.2 mmol), iodine (2 equiv)ꢀTBHP in
H2O (0.6 mmol) and toluene (2 mL). The resulting reaction
yellow liquid. H NMR (400 MHz, CDCl3) δ 2.36 (s, 3H), 6.88
(d, J = 15.6 Hz, 1H), 7.23−7.24 (m, 1H), 7.28−7.31 (m, 3H),
7.54−7.64 (m, 3H), 7.68 (d, J = 15.6 Hz, 1H), 7.96−7.98 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 21.3, 125.9, 127.0, 127.6, 129.0,
129.2, 129.4, 132.1, 132.3, 133.4, 138.9, 140.8, 142.7; LRMS:
m/z calcd for C15H14O2S (M + H): 259.1, found: 259.0.
o
mixture was kept stirring at 90 C for 12 h. Upon completion of
the reaction, the reaction mixture was cooled to room
temperature. After removal of the solvent, the residue was
subjected to column chromatography on silica gel using ethyl
acetate and petroleum ether mixtures to afford the desired
product in high purity.
(E)-1-nitro-4-(2-(phenylsulfonyl)vinyl)benzene (3h). Pale
1
yellow solid, mp = 173 − 175 °C. H NMR (400 MHz, CDCl3) δ
7.05 (d, J = 15.6 Hz, 1H), 7.59−7.62 (m, 2H), 7.66−7.70 (m, 3H),
7.74 (d, J = 15.6 Hz, 1H), 7.97−7.99 (m, 2H), 8.26 (d, J = 8.8 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 124.3, 127.9, 129.3, 129.6,
131.7, 134.0, 138.4, 139.3, 139.8, 149.0; LRMS: m/z calcd for
C14H11NO4S (M + H): 290.0, found: 290.0.
(E)-(2-(phenylsulfonyl)vinyl)benzene (3a). Pale yellow liquid.
1H NMR (400 MHz, CDCl3) δ 6.90 (d, J = 16.0 Hz, 1H),
7.37−7.45 (m, 3H), 7.48−7.51 (m, 2H), 7.54−7.58 (m, 2H),
7.61−7.65 (m, 1H), 7.71 (d, J = 16.0 Hz, 1H), 7.96−7.99 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 127.2, 127.7, 128.6, 129.1, 129.4,
131.3, 132.4, 133.4, 140.7, 142.5; LRMS: m/z calcd for
C14H12O2S (M + H): 245.1, found: 245.1.
(E)-1-fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (3i). Pale
1
yellow liquid. H NMR (400 MHz, CDCl3) δ 6.82 (d, J = 15.6
Hz, 1H), 7.10 (t, J = 8.4 Hz, 2H), 7.48−7.69 (m, 6H), 7.95−7.98
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 116.4 (d, J = 21.0 Hz),
127.0 (d, J = 2.0 Hz), 128.5 (d, J = 174.0 Hz), 128.6 (d, J = 3.0
(E)-1-methoxy-3-(2-(phenylsulfonyl)vinyl)benzene (3b). White
solid, mp = 112 − 115 °C. 1H NMR (400 MHz, CDCl3) δ 3.82 (s,

5
Hz), 130.7 (d, J = 7.0 Hz), 133.5, 140.6, 141.2, 163.1, 165.6;
LRMS: m/z calcd for C14H11FO2S (M + H): 263.0, found: 263.0.
275.0.
ACCEPTED MANUSCRIPT
(E)-1-methyl-4-(styrylsulfonyl)benzene (3q). Pale yellow
1
(E)-1-(2-(phenylsulfonyl)vinyl)-4-(trifluoromethyl)benzene
(3j). Pale yellow solid, mp = 133 − 135 °C. H NMR (400 MHz,
liquid. H NMR (400 MHz, CDCl3) δ 2.46 (s, 3H), 6.87 (d, J =
1
15.2 Hz, 1H), 7.36−7.44 (m, 5H), 7.49−7.51 (m, 2H), 7.68 (d, J =
15.6 Hz, 1H), 7.85 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 21.6, 127.6, 127.7, 128.5, 129.1, 130.0, 131.1, 132.5,
137.7, 142.0, 144.4; LRMS: m/z calcd for C15H15O2S (M + H):
259.1, found: 259.0.
CDCl3) δ 6.98 (d, J = 15.6 Hz, 1H), 7.58−7.68 (m, 7H), 7.73 (d, J
= 15.2 Hz, 1H), 7.97−7.99 (m, 2H); 13C NMR (100 MHz, CDCl3)
δ 123.6 (d, J = 270.0 Hz), 126.1 (q, J = 3.5 Hz), 127.8, 128.8,
129.5, 130.0, 132.6 (q, J = 32.5.0 Hz), 133.8, 135.7, 140.1, 140.5;
LRMS: m/z calcd for C15H11F3O2S (M + H): 313.0, found: 313.0.
(E)-1-nitro-4-(styrylsulfonyl)benzene (3r). Pale yellow liquid.
1H NMR (400 MHz, CDCl3) δ 6.89 (d, J = 15.6 Hz, 1H),
7.41−7.50 (m, 3H), 7.52−7.54 (m, 2H), 7.79 (d, J = 15.2 Hz, 1H),
8.17 (d, J = 8.8 Hz, 2H), 8.40 (d, J = 8.8 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 124.6, 125.6, 128.9, 129.1, 129.3, 131.8, 131.9,
145.0, 146.5, 150.5; LRMS: m/z calcd for C14H11NO4S (M + H):
290.0, found: 290.0.
(E)-1-chloro-4-(2-(phenylsulfonyl)vinyl)benzene (3k). White
solid, mp = 127 − 130 °C. 1H NMR (400 MHz, CDCl3) δ 6.88 (d,
J = 15.2 Hz, 1H), 7.36 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.8 Hz,
2H), 7.55−7.58 (m, 2H), 7.62−7.67 (m, 2H), 7.95−7.97 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 127.7, 127.9, 129.4, 129.4, 129.8,
130.9, 133.6, 137.2, 140.5, 141.0; LRMS: m/z calcd for
C14H11ClO2S (M + H): 279.0, found: 279.0.
(E)-1-chloro-4-(styrylsulfonyl)benzene (3s). White solid, mp =
1
(E)-1-methyl-4-(2-(phenylsulfonyl)vinyl)benzene (3l). White
solid, mp = 130 − 132 °C. 1H NMR (400 MHz, CDCl3) δ 2.38 (s,
3H), 6.84 (d, J = 15.2 Hz, 1H), 7.21 (d, J = 8.0 Hz, 2H), 7.39 (d,
J = 8.0 Hz, 2H), 7.56 (t, J = 7.6 Hz, 2H), 7.61−7.66 (m, 1H), 7.68
(d, J = 15.6 Hz, 1H), 7.97 (d, J = 7.2 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 21.5, 126.1, 127.6, 128.6, 129.3, 129.6, 129.8,
133.3, 140.9, 141.9, 142.6; LRMS: m/z calcd for C15H14O2S (M +
H): 259.1, found: 259.0.
78 − 80 °C. H NMR (400 MHz, CDCl3) δ 6.87 (d, J = 15.6 Hz,
1H), 7.39−7.47 (m, 3H), 7.49−7.55 (m, 4H), 7.71 (d, J = 15.2 Hz,
1H), 7.90 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
126.8, 128.7, 129.2, 129.7, 131.5, 132.2, 139.2, 140.1, 143.1;
LRMS: m/z calcd for C14H11ClO2S (M + H): 279.0, found: 279.0.
(E)-1-bromo-4-(styrylsulfonyl)benzene (3t). White solid, mp =
98 − 100 °C. 1H NMR (400 MHz, CDCl3) δ 6.86 (d, J = 15.2 Hz,
1H), 7.39−7.47 (m, 3H), 7.49−7.52 (m, 2H), 7.69−7.73 (m, 3H),
7.83 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 126.8,
128.7, 129.2, 129.3, 131.5, 132.2, 132.7, 139.8, 143.2; LRMS:
m/z calcd for C14H11BrO2S (M + H): 323.0, found: 323.0.
(E)-1-isopropyl-4-(2-(phenylsulfonyl)vinyl)benzene
(3m).
1
White solid, mp = 98 − 100 °C. H NMR (400 MHz, CDCl3) δ
1.22 (s, 3H), 1.24 (s, 3H), 2.87−2.94 (m, 1H), 6.84 (d, J = 15.2
Hz, 1H), 7.24 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H),
7.51−7.55 (m, 2H), 7.57−7.62 (m, 1H), 7.67 (d, J = 15.2 Hz, 1H),
7.94−7.97 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 23.7, 34.1,
126.2, 127.2, 127.6, 128.8, 129.3, 130.0, 133.3, 141.0, 142.6,
152.8; LRMS: m/z calcd for C17H18O2S (M + H): 287.1, found:
287.1.
(E)-2-(styrylsulfonyl)naphthalene (3u). White solid, mp = 138
− 140 °C. H NMR (400 MHz, CDCl3) δ 6.95 (d, J = 15.6 Hz,
1
1H), 7.38−7.46 (m, 3H), 7.50−7.53 (m, 2H), 7.63−7.71 (m, 2H),
7.77 (d, J = 15.2 Hz, 1H), 7.90−7.95 (m, 2H), 8.00−8.03 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 122.6, 127.3, 127.7, 128.0, 128.6,
129.1, 129.2, 129.3, 129.4, 129.7, 131.3, 132.3, 132.4, 135.2,
137.5, 142.6; LRMS: m/z calcd for C18H14O2S (M + H): 295.1,
found: 295.0.
(E)-1-(2-(phenylsulfonyl)vinyl)naphthalene (3n). White solid,
1
mp = 99 − 101 °C. H NMR (400 MHz, CDCl3) δ 6.97 (d, J =
15.2 Hz, 1H), 7.46 (t, J = 7.8 Hz, 1H), 7.54−7.68 (m, 6H), 7.91
(dd, J = 14.8 Hz, 8.0, 2H), 8.01 (d, J = 7.2 Hz , 2H), 8.17 (d, J =
8.4 Hz, 1H), 8.54 (d, J = 15.2 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 123.0, 125.3, 125.8, 126.6, 127.4, 127.8, 128.9, 129.4,
129.5, 129.6, 131.3, 131.5, 133.5, 133.7, 139.6, 140.6; LRMS:
m/z calcd for C18H14O2S (M + H): 295.1, found: 295.0.
(E)-1-(styrylsulfonyl)-4-(trifluoromethyl)benzene (3v). White
solid, mp = 125 − 127 °C. 1H NMR (400 MHz, CDCl3) δ 6.88 (d,
J = 15.4 Hz, 1H), 7.40−7.49 (m, 3H), 7.51−7.55 (m, 2H), 7.77 (d,
J = 15.6 Hz, 1H), 7.84 (d, J = 8.0 Hz, 2H), 8.12 (d, J = 8.0 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 123.2 (d, J = 272.0 Hz),
126.2, 126.5 (q, J = 3.5 Hz), 128.3, 128.8, 129.2, 131.7, 132.0,
135.1 (q, J = 32.5 Hz), 144.1, 144.4; LRMS: m/z calcd for
C15H11F3O2S (M + H): 313.0, found: 313.0.
(E)-2-(2-(phenylsulfonyl)vinyl)thiophene (3o). Pale yellow
liquid. 1H NMR (400 MHz, CDCl3) δ 6.67 (d, J = 15.2 Hz, 1H),
7.07−7.09 (m, 1H), 7.33 (d, J = 3.6 Hz, 1H), 7.45 (d, J = 4.8 Hz,
1H), 7.54−7.58 (m, 2H ), 7.61−7.65 (m, 1H), 7.81 (d, J = 15.2
Hz, 1H), 7.94−7.96 (m, 2H); 13C NMR (100 MHz, CDCl3) δ
125.4, 127.6, 128.4, 129.4, 130.1, 132.5, 133.4, 135.2, 136.9,
140.8; LRMS: m/z calcd for C12H10O2S2 (M + H): 251.0, found:
251.0.
(E)-1,3-dimethoxy-5-(2-(phenylsulfonyl)vinyl)benzene (3w).
1
Pale yellow solid, mp = 125 − 127 °C. H NMR (400 MHz,
CDCl3) δ 3.80 (s, 6H), 6.52 (t, J = 2.2 Hz, 1H), 6.63 (d, J = 2.4
Hz 2H), 6.87 (d, J = 15.6 Hz, 1H), 7.54−7.65 (m, 4H), 7.95−7.97
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 55.5, 103.4, 106.5,
127.7, 127.7, 129.4, 133.5, 134.1, 140.6, 142. 6, 161.1; LRMS:
m/z calcd for C16H16O4S (M + H): 305.1, found: 305.1.
(E)-1-methoxy-4-(styrylsulfonyl)benzene (3p). Pale yellow
solid, mp = 108 − 110 °C. 1H NMR (400 MHz, CDCl3) δ 3.87 (s,
3H), 6.87 (d, J = 15.2 Hz, 1H), 7.02 (d, J = 9.2 Hz, 2H),
7.36−7.42 (m, 3H), 7.47−7.49 (m, 2H), 7.64 (d, J = 15.6 Hz, 1H),
7.89 (d, J = 9.2 Hz, 2H ); 13C NMR (100 MHz, CDCl3) δ 55.7,
114.6, 127.9, 128.5, 129.1, 129.9, 131.1, 132.2, 132.5, 141.4,
163.6; LRMS: m/z calcd for C15H14O3S (M + H): 275.1, found:
Acknowledgments
We are grateful to the grants from the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, State

6
Education Ministry, the Priority Academic Program Development of
Jiangsu Higher Education Institutions, and the Key Laboratory of
Organic Synthesis of Jiangsu Province
ACCEPTED MANUSCRIPT
References and notes
1. Miller, R. D.; Hassig, R. Tetrahedron Lett. 1985, 26, 2395.
2. a) Meadows, D. C.; Gervay-Hague, J. Med. Res. Rev. 2006, 26,
793; b) Lopez-Jaramillo,F. J.; Ortega-Muñoz,M.;
Megia-Fernandez, A.; Hernandez-Mateo, F.; Santoyo-Gonzalez, F.
Bioconjugate Chem. 2012, 23, 846.
3. a) Taniguchi, N. Synlett 2012, 23, 1245; b) Xue, Q. ; Mao, Z. ;
Shi, Y.; Mao, H.; Cheng, Y.; Zhu, C. Tetrahedron Lett. 2012, 53,
1851; c) Ruano, J. L. G.; Alemán, J.; Paredes, C. G. Org. Lett.
2006, 8, 2683.
4. a) Nair, V.; Augustine, A.; George, T. G.; Nair, L. G. Tetrahedron
Lett. 2001, 42, 6763; b) Katrun, P.; Chiampanichayakul, S.;
Korworapan, K.; Pohmakotr, M.; Reutrakul, V.; Jaipetch, T.;
Kuhakarn, C. Eur. J. Org. Chem. 2010, 5633; c) Kamigata, N.;
Sawada, H.; Kobayashi, M. J. Org. Chem. 1983, 48, 3793; d)
Taniguchi, N. Synlett 2011, 1308; e) Nair, V.; Augustine, A.; Suja,
T. D. Synthesis 2002, 2259; f) Das, B.; Lingaiah, M.; Damodar, K.;
Bhunia, N. Synthesis 2011, 2941; g) Sawangphon, T.; Katrun, P.;
Chaisiwamongkhol, K.; Pohmakotr, M.; Reutrakul, V.; Jaipetch,
T.; Soorukram, D.; Kuhakarn, C. Synth. Commun. 2013, 43, 1692.
5. a) Russell, G. A.; Ngoviwatchai, P.; Tashtoush, H. I.; Pla-Dalmau,
A.; Khanna, R. K. J. Am. Chem. Soc. 1988, 110, 3530; b) Bian, M.;
Xu, F.; Ma, C. Synthesis 2007, 2951.
6. Huang, F.; Batey, R. A. Tetrahedron 2007, 63, 7667.
7. Reeves, D. C.; Rodriguez, S.; Lee, H.; Hahhad, N.;
Krishnamurthy, D.; Senanayake, C. H. Tetrahedron Lett. 2009, 50,
2870.
8. Chawla, R.; Kapoor, R.; Singh, A. K.; Yadav, L. D. S. Green
Chem. 2012, 14, 1308.
9. Selected examples: a) Rodríguez, N.; Goossen, L. J. Chem. Soc.
Rev. 2011, 40, 5030; b) Dzik, W. I.; Lange, P. P.; Goossen, L. J.
Chem. Sci. 2012, 3, 2671; c) Goossen, L. J.; Rodríguez, N.;
Goossen, K. Angew. Chem., Int. Ed. 2008, 47, 3100; d) Hu, P.;
Zhang, M.; Jie, X.; Su, W. Angew. Chem., Int. Ed. 2012, 51, 227;
e) Hu, P.; Shang, Y. P.; Su, W. Angew. Chem., Int. Ed. 2012, 51,
5945; f) Shang, R.; Xu, Q.; Jiang, Y.; Wang, Y.; Liu, L. Org. Lett.
2010, 12, 1000; g) Shang, R.; Xu, Q.; Jiang, Y.; Wang, Y.; Liu, L.
Org. Lett. 2010, 12, 1000; h) Shang, R.; Huang, Z.; Chu, L.; Fu,
Y.; Liu, L. Org. Lett. 2011, 13, 4240; i) Cornella, J.; Lahlali, H.;
Larrosa, I. Chem. Commun. 2010, 46, 8276.
10. Selected examples: a) Jia, W.; Jiao, N. Org. Lett. 2010, 12, 2000;
b) Zhang, Y.; Patel, S.; Mainolfi, N. Chem. Sci. 2012, 3, 3196; c)
Pandey, G.; Bhowmik, S.; Batra, S. Org. Lett. 2013, 15, 5044; d)
Priebbenow, D. L.; Becker, P.; Bolm, C. Org. Lett. 2013, 15, 6155;
e) Song, Q.; Feng, Q.; Yang, K. Org. Lett. 2014, 16, 624.
11. Selected examples: a) Hu, J.; Zhao, N.; Yang, B.; Wang, G.; Guo,
L.-N.; Liang, Y.-M.; Yang, S.-D. Chem.-Eur. J. 2011 , 17, 5516;
b) Li, X.; Yang, F.; Wu, Y. Org. Lett. 2014, 16, 992.
12. Duan, Z.; Ranjit, S.; Zhang, P.; Liu, X. Chem.-Eur. J. 2009, 15,
3666.
13. Ranjit, S.; Duan, Z.; Zhang, P.; Liu, X. Org. Lett. 2010, 12, 4134.
14. Becht, J.-M.; Drian, C. L. J. Org. Chem. 2011, 76, 6327.
15. Wang, P.-F.; Wang, X.-Q.; Dai, J.-J.; Feng, Y.-S.; Xu, H.-J. Org.
Lett. 2014, 16, 4586.
16. a) Jiang, Q.; Xu, B.; Jia, J.; Zhao, A.; Zhao, Y.-R.; Li, Y.-Y.; He,
N.-N.; Guo, C.-C. J. Org. Chem. 2014, 79, 7372; b) Rokade, B. V.;
Prabhu, K. R. J. Org. Chem. 2014, 79, 8110; c) Guo, R.; Gui, Q.;
Wang, D.; Tan, Z. Catal. Lett. 2014, 144, 1377; d) Li, H.-S.; Liu,
G. J. Org. Chem. 2014, 79, 509; e) Xu, Y.; Tang, X.; Hu, W.; Wu,
W.; Jiang, H. Green Chem. 2014, 16, 3720.
17. a) Yang, H.; Sun, P.; Zhu, Y.; Yan, H.; Lu, L.; Qu. X.; Li. T.;
Mao, J. Chem. Commun. 2012, 48, 7847; b) Yang, H.; Yan, H.;
Sun, P.; Zhu, Y.; Lu, L.; Liu, D.; Rong, G.; Mao, J. Green Chem.
2013, 15, 976; c) Yan, H.; Lu, L.; Rong, G.; Liu, D.; Zheng, Y.;
Chen, J.; Mao, J. J. Org. Chem. 2014, 79, 7103; d) Rong, G.; Liu,
D.; Lu, L.; Yan, H.; Zheng, Y.; Chen, J.; Mao, J. Tetrahedron
2014, 70, 5033.
18. Xiao, F.; Chen, H.; Xie, H.; Chen, S.; Yang, L.; Deng, G.-J. Org.
Lett. 2014, 16, 50.

ACCEPTED MANUSCRIPT
SUPPORTING INFORMATION
Iodine-Promoted Decarboxylative C−S
Cross-Coupling of Cinnamic Acids with Sodium
Benzene Sulfinates
Jie Chena, Jincheng Mao,a,b,* Yang Zhenga, Defu Liua, Guangwei ronga, Hong Yan,a
Cheng Zhanga, Daqing Shia,*
aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical
Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
bState Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum
University, Chengdu, 610500, P. R. China
Table of Contents
1. General information
S2
S3-S6
2. Characterization of the corresponding products
3. NMR Spectra
S7-S29
-S1-

ACCEPTED MANUSCRIPT
General Procedures
General experimental: All reactions were carried out under air. Solvents were dried and
degassed by standard methods. Flash column chromatography was performed using silica gel
(300-400 mesh). Analytical thin-layer chromatography was performed using glass plates
pre-coated with 200-400 mesh silica gel impregnated with a fluorescent indicator (254 nm). NMR
spectra were measured in CDCl3 on a Varian Inova-400 NMR spectrometer (400 MHz or 300
MHz) with TMS as an internal reference. Products were characterized by comparison of 1H NMR,
13C NMR and TOF-MS data in the literature.
-S2-

ACCEPTED MANUSCRIPT
Characterization of the corresponding products:
(E)-(2-(phenylsulfonyl)vinyl)benzene (3a)
1
Pale yellow liquid. H NMR (400 MHz, CDCl3) δ 6.90 (d, J = 16.0 Hz, 1H), 7.37−7.45 (m, 3H),
7.48−7.51 (m, 2H), 7.54−7.58 (m, 2H), 7.61−7.65 (m, 1H), 7.71 (d, J = 16.0 Hz, 1H), 7.96−7.99
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 127.2, 127.7, 128.6, 129.1, 129.4, 131.3, 132.4, 133.4,
140.7, 142.5; LRMS: m/z calcd for C14H12O2S (M + H): 245.1, found: 245.1.
(E)-1-methoxy-3-(2-(phenylsulfonyl)vinyl)benzene (3b)
White solid, mp: 112 − 115 °C. 1H NMR (400 MHz, CDCl3) δ 3.82 (s, 3H), 6.88 (d, J = 15.2 Hz,
1H), 6.96−7.01 (m, 2H), 7.09 (d, J = 7.6 Hz, 1H), 7.30 (t, J = 7.8 Hz, 1H), 7.54 (t, J = 7.6 Hz, 2H),
7.61 (d, J = 7.2 Hz, 1H), 7.65 (d, J = 15.6 Hz, 1H), 7.94−7.96 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 55.4, 113.4, 117.2, 121.2, 127.6, 127.7, 129.4, 130.1, 133.4, 133.7, 140.7, 142.5, 160.0;
LRMS: m/z calcd for C15H14O3S (M + H): 275.1, found: 275.1
(E)-5-(2-(phenylsulfonyl)vinyl)benzo[d][1,3]dioxole (3c)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 6.01 (s, 6H), 6.69 (d, J = 15.2 Hz, 1H), 6.82 (d,
J = 8.1 Hz, 1H), 6.95 (d, J = 1.6 Hz, 1H), 6.99−7.02 (dd, J = 1.6, 8.0 Hz, 1H ), 7.53−7.64 (m, 4H),
7.93−7.95 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 101.8, 106.8, 108.7, 125.0, 125.4, 126.6, 127.5,
129.3, 133.3, 141.0, 142.3, 148.5, 150.4; LRMS: m/z calcd for C15H12O4S (M + H): 289.0, found:
289.0.
(E)-1-methoxy-4-(2-(phenylsulfonyl)vinyl)benzene (3d)
White solid, mp: 108 − 110 °C. 1H NMR (400 MHz, CDCl3) δ 3.82 (s, 3H), 6.74 (d, J = 15.6 Hz,
1H), 6.90 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.8 Hz, 2H), 7.52−7.60 (m, 3H), 7.64 (d, J = 15.2 Hz,
1H), 7.95 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 55.5, 114.5, 124.4, 125.0, 127.5,
129.3, 130.4, 133.2, 141.1, 142.3, 162.1; LRMS: m/z calcd for C15H14O3S (M + H): 275.1, found:
275.0.
(E)-1,2-dimethoxy-4-(2-(phenylsulfonyl)vinyl)benzene (3e)
White solid, mp: 153 − 154 °C. 1H NMR (400 MHz, CDCl3) δ 3.87 (s, 3H), 3.89 (s, 3H), 6.77 (d,
J = 15.6 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.99 (d, J = 2.0 Hz, 1H), 7.09 (dd, J = 8.4, 2.0 Hz, 1H),
7.51−7.64 (m, 4H), 7.93−7.96 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 55.9, 56.0, 110.0, 111.1,
123.6, 124.7, 125.2, 127.5, 129.3, 133.2, 141.1, 142.6, 149.3, 151.9; LRMS: m/z calcd for
C16H16O4S (M + H): 305.1, found: 305.1.
(E)-1,2,3-trimethoxy-5-(2-(phenylsulfonyl)vinyl)benzene (3f)
1
Pale yellow solid, mp: 165 − 167 °C. H NMR (400 MHz, CDCl3) δ 3.85 (s, 6H), 3.85 (s, 3H),
6.73 (s, 2H), 6.84 (d, J = 15.2 Hz, 1H), 7.52−7.63 (m, 4H), 7.93−7.95 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 56.2, 61.0, 105.9, 126.4, 127.6, 127.8, 129.4, 133.4, 140.8, 142.6, 153.5; LRMS:
m/z calcd for C17H18O5S (M + H): 335.1, found: 335.1.
(E)-1-methyl-3-(2-(phenylsulfonyl)vinyl)benzene (3g)
-S3-

ACCEPTED MANUSCRIPT
1
Pale yellow liquid. H NMR (400 MHz, CDCl3) δ 2.36 (s, 3H), 6.88 (d, J = 15.6 Hz, 1H),
7.23−7.24 (m, 1H), 7.28−7.31 (m, 3H), 7.54−7.64 (m, 3H), 7.68 (d, J = 15.6 Hz, 1H), 7.96−7.98
(m, 2H); 13C NMR (100 MHz, CDCl3) δ 21.3, 125.9, 127.0, 127.6, 129.0, 129.2, 129.4, 132.1,
132.3, 133.4, 138.9, 140.8, 142.7; LRMS: m/z calcd for C15H14O2S (M + H): 259.1, found: 259.0.
(E)-1-nitro-4-(2-(phenylsulfonyl)vinyl)benzene (3h)
1
Pale yellow solid, mp: 173 − 175 °C. H NMR (400 MHz, CDCl3) δ 7.05 (d, J = 15.6 Hz, 1H),
7.59−7.62 (m, 2H), 7.66−7.70 (m, 3H), 7.74 (d, J = 15.6 Hz, 1H), 7.97−7.99 (m, 2H), 8.26 (d, J =
8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 124.3, 127.9, 129.3, 129.6, 131.7, 134.0, 138.4, 139.3,
139.8, 149.0; LRMS: m/z calcd for C14H11NO4S (M + H): 290.0, found: 290.0.
(E)-1-fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (3i)
1
Pale yellow liquid. H NMR (400 MHz, CDCl3) δ 6.82 (d, J = 15.6 Hz, 1H), 7.10 (t, J = 8.4 Hz,
2H), 7.48−7.69 (m, 6H), 7.95−7.98 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 116.4 (d, J = 21.0
Hz), 127.0 (d, J = 2.0 Hz), 128.5 (d, J = 174.0 Hz), 128.6 (d, J = 3.0 Hz), 130.7 (d, J = 7.0 Hz),
133.5, 140.6, 141.2, 163.1, 165.6; LRMS: m/z calcd for C14H11FO2S (M + H): 263.0, found:
263.0.
(E)-1-(2-(phenylsulfonyl)vinyl)-4-(trifluoromethyl)benzene (3j)
1
Pale yellow solid, mp: 133 − 135 °C. H NMR (400 MHz, CDCl3) δ 6.98 (d, J = 15.6 Hz, 1H),
7.58−7.68 (m, 7H), 7.73 (d, J = 15.2 Hz, 1H), 7.97−7.99 (m, 2H); 13C NMR (100 MHz, CDCl3) δ
123.6 (d, J = 270.0 Hz), 126.1 (q, J = 3.5 Hz), 127.8, 128.8, 129.5, 130.0, 132.6 (q, J = 32.5.0 Hz),
133.8, 135.7, 140.1, 140.5; LRMS: m/z calcd for C15H11F3O2S (M + H): 313.0, found: 313.0.
(E)-1-chloro-4-(2-(phenylsulfonyl)vinyl)benzene (3k)
White solid, mp: 127 − 130 °C. 1H NMR (400 MHz, CDCl3) δ 6.88 (d, J = 15.2 Hz, 1H), 7.36 (d,
J = 8.4 Hz, 2H), 7.43 (d, J = 8.8 Hz, 2H), 7.55−7.58 (m, 2H), 7.62−7.67 (m, 2H), 7.95−7.97 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 127.7, 127.9, 129.4, 129.4, 129.8, 130.9, 133.6, 137.2, 140.5,
141.0; LRMS: m/z calcd for C14H11ClO2S (M + H): 279.0, found: 279.0.
(E)-1-methyl-4-(2-(phenylsulfonyl)vinyl)benzene (3l)
White solid, mp: 130 − 132 °C. 1H NMR (400 MHz, CDCl3) δ 2.38 (s, 3H), 6.84 (d, J = 15.2 Hz,
1H), 7.21 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 7.56 (t, J = 7.6 Hz, 2H), 7.61−7.66 (m, 1H),
13
7.68 (d, J = 15.6 Hz, 1H), 7.97 (d, J = 7.2 Hz, 2H); C NMR (100 MHz, CDCl3) δ 21.5, 126.1,
127.6, 128.6, 129.3, 129.6, 129.8, 133.3, 140.9, 141.9, 142.6; LRMS: m/z calcd for C15H14O2S (M
+ H): 259.1, found: 259.0.
(E)-1-isopropyl-4-(2-(phenylsulfonyl)vinyl)benzene (3m)
White solid, mp: 98 − 100 °C. 1H NMR (400 MHz, CDCl3) δ 1.22 (s, 3H), 1.24 (s, 3H), 2.87−2.94
(m, 1H), 6.84 (d, J = 15.2 Hz, 1H), 7.24 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 7.51−7.55
(m, 2H), 7.57−7.62 (m, 1H), 7.67 (d, J = 15.2 Hz, 1H), 7.94−7.97 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 23.7, 34.1, 126.2, 127.2, 127.6, 128.8, 129.3, 130.0, 133.3, 141.0, 142.6, 152.8; LRMS:
m/z calcd for C17H18O2S (M + H): 287.1, found: 287.1.
(E)-1-(2-(phenylsulfonyl)vinyl)naphthalene (3n)
-S4-

ACCEPTED MANUSCRIPT
White solid, mp: 99 − 101 °C. 1H NMR (400 MHz, CDCl3) δ 6.97 (d, J = 15.2 Hz, 1H), 7.46 (t, J
= 7.8 Hz, 1H), 7.54−7.68 (m, 6H), 7.91 (dd, J = 14.8, 8.0 Hz, 2H), 8.01 (d, J = 7.2 Hz, 2H), 8.17
(d, J = 8.4 Hz, 1H), 8.54 (d, J = 15.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 123.0, 125.3, 125.8,
126.6, 127.4, 127.8, 128.9, 129.4, 129.5, 129.6, 131.3, 131.5, 133.5, 133.7, 139.6, 140.6; LRMS:
m/z calcd for C18H14O2S (M + H): 295.1, found: 295.0.
(E)-2-(2-(phenylsulfonyl)vinyl)thiophene (3o)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3) δ 6.67 (d, J = 15.2 Hz, 1H), 7.07−7.09 (m, 1H),
7.33 (d, J = 3.6 Hz, 1H), 7.45 (d, J = 4.8 Hz, 1H), 7.54−7.58 (m, 2H ), 7.61−7.65 (m, 1H), 7.81 (d,
J = 15.2 Hz, 1H), 7.94−7.96 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 125.4, 127.6, 128.4, 129.4,
130.1, 132.5, 133.4, 135.2, 136.9, 140.8; LRMS: m/z calcd for C12H10O2S2 (M + H): 251.0, found:
251.0.
(E)-1-methoxy-4-(styrylsulfonyl)benzene (3p)
Pale yellow solid, mp: 108 − 110 °C. 1H NMR (400 MHz, CDCl3) δ 3.87 (s, 3H), 6.87 (d, J = 15.2
Hz, 1H), 7.02 (d, J = 9.2 Hz, 2H), 7.36−7.42 (m, 3H), 7.47−7.49 (m, 2H), 7.64 (d, J = 15.6 Hz,
1H), 7.89 (d, J = 9.2 Hz, 2H ); 13C NMR (100 MHz, CDCl3) δ 55.7, 114.6, 127.9, 128.5, 129.1,
129.9, 131.1, 132.2, 132.5, 141.4, 163.6; LRMS: m/z calcd for C15H14O3S (M + H): 275.1, found:
275.0.
(E)-1-methyl-4-(styrylsulfonyl)benzene (3q)
1
Pale yellow liquid. H NMR (400 MHz, CDCl3) δ 2.46 (s, 3H), 6.87 (d, J = 15.2 Hz, 1H),
7.36−7.44 (m, 5H), 7.49−7.51 (m, 2H), 7.68 (d, J = 15.6 Hz, 1H), 7.85 (d, J = 8.0 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ 21.6, 127.6, 127.7, 128.5, 129.1, 130.0, 131.1, 132.5, 137.7, 142.0,
144.4; LRMS: m/z calcd for C15H15O2S (M + H): 259.1, found: 259.0.
(E)-1-nitro-4-(styrylsulfonyl)benzene (3r)
1
Pale yellow liquid. H NMR (400 MHz, CDCl3) δ 6.89 (d, J = 15.6 Hz, 1H), 7.41−7.50 (m, 3H),
7.52−7.54 (m, 2H), 7.79 (d, J = 15.2 Hz, 1H), 8.17 (d, J = 8.8 Hz, 2H), 8.40 (d, J = 8.8 Hz, 2H);
13C NMR (100 MHz, CDCl3) δ 124.6, 125.6, 128.9, 129.1, 129.3, 131.8, 131.9, 145.0, 146.5,
150.5; LRMS: m/z calcd for C14H11NO4S (M + H): 290.0, found: 290.0.
(E)-1-chloro-4-(styrylsulfonyl)benzene (3s)
White solid, mp: 78 − 80 °C. 1H NMR (400 MHz, CDCl3) δ 6.87 (d, J = 15.6 Hz, 1H), 7.39−7.47
13
(m, 3H), 7.49−7.55 (m, 4H), 7.71 (d, J = 15.2 Hz, 1H), 7.90 (d, J = 8.8 Hz, 2H); C NMR (100
MHz, CDCl3) δ 126.8, 128.7, 129.2, 129.7, 131.5, 132.2, 139.2, 140.1, 143.1; LRMS: m/z calcd
for C14H11ClO2S (M + H): 279.0, found: 279.0.
(E)-1-bromo-4-(styrylsulfonyl)benzene (3t)
White solid, mp: 98 − 100 °C. 1H NMR (400 MHz, CDCl3) δ 6.86 (d, J = 15.2 Hz, 1H), 7.39−7.47
13
(m, 3H), 7.49−7.52 (m, 2H), 7.69−7.73 (m, 3H), 7.83 (d, J = 8.8 Hz, 2H); C NMR (100 MHz,
CDCl3) δ 126.8, 128.7, 129.2, 129.3, 131.5, 132.2, 132.7, 139.8, 143.2; LRMS: m/z calcd for
C14H11BrO2S (M + H): 323.0, found: 323.0.
(E)-2-(styrylsulfonyl)naphthalene (3u)
-S5-

ACCEPTED MANUSCRIPT
1
White solid, mp: 138 − 140 °C. H NMR (400 MHz, CDCl3) δ 6.95 (d, J = 15.6 Hz, 1H),
7.38−7.46 (m, 3H), 7.50−7.53 (m, 2H), 7.63−7.71 (m, 2H), 7.77 (d, J = 15.2 Hz, 1H), 7.90−7.95
(m, 2H), 8.00−8.03 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 122.6, 127.3, 127.7, 128.0, 128.6,
129.1, 129.2, 129.3, 129.4, 129.7, 131.3, 132.3, 132.4, 135.2, 137.5, 142.6; LRMS: m/z calcd for
C18H14O2S (M + H): 295.1, found: 295.0.
(E)-1-(styrylsulfonyl)-4-(trifluoromethyl)benzene (3v)
1
White solid, mp: 125 − 127 °C. H NMR (400 MHz, CDCl3) δ 6.88 (d, J = 15.4 Hz, 1H),
7.40−7.49 (m, 3H), 7.51−7.55 (m, 2H), 7.77 (d, J = 15.6 Hz, 1H), 7.84 (d, J = 8.0 Hz, 2H), 8.12 (d,
J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 123.2 (d, J = 272.0 Hz), 126.2, 126.5 (q, J = 3.5
Hz), 128.3, 128.8, 129.2, 131.7, 132.0, 135.1 (q, J = 32.5 Hz), 144.1, 144.4; LRMS: m/z calcd for
C15H11F3O2S (M + H): 313.0, found: 313.0.
(E)-1,3-dimethoxy-5-(2-(phenylsulfonyl)vinyl)benzene (3w)
Pale yellow solid, mp: 125 − 127 °C. 1H NMR (400 MHz, CDCl3) δ 3.80 (s, 6H), 6.52 (t, J = 2.2
Hz, 1H), 6.63 (d, J = 2.4 Hz 2H), 6.87 (d, J = 15.6 Hz, 1H), 7.54−7.65 (m, 4H), 7.95−7.97 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 55.5, 103.4, 106.5, 127.7, 127.7, 129.4, 133.5, 134.1, 140.6,
142. 6, 161.1; LRMS: m/z calcd for C16H16O4S (M + H): 305.1, found: 305.1.
-S6-

ACCEPTED MANUSCRIPT
Copy of NMR Spectra for desired products:
-S7-

ACCEPTED MANUSCRIPT
-S8-

ACCEPTED MANUSCRIPT
-S9-

ACCEPTED MANUSCRIPT
-S10-

ACCEPTED MANUSCRIPT
-S11-

ACCEPTED MANUSCRIPT
-S12-

ACCEPTED MANUSCRIPT
-S13-

ACCEPTED MANUSCRIPT
-S14-

ACCEPTED MANUSCRIPT
-S15-

ACCEPTED MANUSCRIPT
-S16-

ACCEPTED MANUSCRIPT
-S17-

ACCEPTED MANUSCRIPT
-S18-

ACCEPTED MANUSCRIPT
-S19-

ACCEPTED MANUSCRIPT
-S20-

ACCEPTED MANUSCRIPT
-S21-

ACCEPTED MANUSCRIPT
-S22-