Gram-scale synthesis of β-sulfonyl styrenes

Article abstract of DOI:10.1055/s-0037-1610822

A simple and gram-scale synthesis of β-sulfonyl styrenes has been developed starting from one-pot PPA (polyphosphoric acid)-catalyzed 1,1-diacetoxylation of arylacetaldehydes (ArCH₂CHO) with acetic anhydride (Ac₂O) followed by deacetoxylative sulfonylation of the resulting 1,1-diacetate intermediate with sodium sulfinates (RSO₂Na) in good yields under solvent-free conditions.

Full text of DOI:10.1055/s-0037-1610822

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2018, 50, A–H
paper
A
en
M.-Y. Chang et al.
Paper
Synthesis
Gram-Scale Synthesis of β-Sulfonyl Styrenes
Meng-Yang Chang*a,b
Yan-Shin Wua
Yu-Ting Hsiaoa
1,1-diacetoxylation/deacetoxylative sulfonylation
O
S
PPA, Ac2O
then NaSO2R
29 examples
O
OAc
OAc
R
a Department of Medicinal and Applied Chemistry,
Kaohsiung Medical University, Kaohsiung 807, Taiwan
mychang@kmu.edu.tw
b Department of Medical Research, Kaohsiung Medical
University Hospital, Kaohsiung 807, Taiwan
Ar
Ar
Ar
O
economical and gram-scale synthesis
41–93% yields
Received: 22.05.2018
Accepted after revision: 25.06.2018
Published online: 08.08.2018
ports, we wanted to develop an economical and gram-scale
synthesis of β-sulfonyl styrenes 1 without air-sensitive con-
ditions and expensive transitional-metal catalysts. Herein,
we disclose a PPA (polyphosphoric acid)-catalyzed 1,1-diac-
etoxylation of arylacetaldehydes 2 (ArCH2CHO) with acetic
anhydride (Ac2O) followed by deacetoxylative sulfonylation
of the resulting 1,1-diacetate intermediate with sodium
sulfinates 3 (RSO2Na) in moderate to good yields on a gram
scale under solvent-free conditions (Scheme 2).17 As far as
we know, there have been no reports on the use of arylacet-
aldehydes serving as the starting materials in the formation
of β-sulfonyl styrenes.
DOI: 10.1055/s-0037-1610822; Art ID: ss-2018-h0361-op
Abstract A simple and gram-scale synthesis of β-sulfonyl styrenes has
been developed starting from one-pot PPA (polyphosphoric acid)-cata-
lyzed 1,1-diacetoxylation of arylacetaldehydes (ArCH2CHO) with acetic
anhydride (Ac2O) followed by deacetoxylative sulfonylation of the re-
sulting 1,1-diacetate intermediate with sodium sulfinates (RSO2Na) in
good yields under solvent-free conditions.
Key words β-sufonyl styrenes, sodium sulfinates, arylacetaldehydes,
gram-scale synthesis
Continuing our research on Brønsted acid mediated syn-
thetic applications,18 herein, PPA was chosen first as the
model promoter to seek optimal reaction conditions for
synthesizing β-sulfonyl styrenes 1 in the presence of Ac2O
by the cross coupling of 3,4-dimethoxyphenylacetaldehyde
(2a) [Ar = 3,4-(MeO)2C6H3] and TolSO2Na (3a) at room tem-
perature. Initially, we checked the solvent system, including
solvent-containing and solvent-free conditions, respective-
ly (Table 1, entries 1–5). When the volume of reaction sol-
vents (MeNO2 or DMAc) was increased gradually (0 → 1 → 2
→ 4 mL), we were surprised to find that the reaction hardly
proceeded in the presence of the solvent, while the reaction
provided the desired 1a in good yield (90%) under the sol-
vent-free conditions. Moreover, product 1a possessed com-
plete E-stereoselectivity. With this idea in mind, four pro-
moters (H2SO4, p-TsOH, AcOH, H3BO3) were examined.
When the reaction mixture was treated with H2SO4 at room
temperature for 1 hour (entry 6), a complex mixture was
isolated. Changing to p-TsOH, 66% of 1a was provided (entry
7). After changing promoters from stronger sulfonic-type
acids to weaker acids, AcOH or H3BO3, the results showed
that 1a was produced in trace amounts (10% or 5%, entries
8, 9). After elevating the temperature (25 → 80 °C), the iso-
Among the sulfur-containing structures, β-sulfonyl sty-
renes (styryl sulfones) have attracted much attention in dif-
ferent fields, resulting in various synthetic strategies for
their applications,1 especially in organic building blocks,2
natural product synthesis,3 bioactive molecules,4 and func-
tionalized emitter materials.5 Conventional synthesis for
this skeleton includes (1) oxidation of vinyl sulfides,6 (2)
elimination of halosulfones,7 (3) Horner–Wadsworth–
Emmons olefination of β-phosphonate sulfones with car-
bonyl compounds,8 and (4) the addition of sulfonyl halides
to alkynes.9 In contrast to these traditional strategies, re-
cent works have focused on various sulfonyl synthon-medi-
ated cross-coupling of aryl substrates with a triple bond (for
arylacetylenes), a double bond (for cinnamic acids, styryl
bromides, boronic acids, or sulfides), and a single bond (for
epoxides, dibromides) under versatile reagent-initiated
conditions (e.g., transition metals, oxidants, bases, acids,
salts, LEDs, solvents, or electrolytes). As shown in Scheme 1,
these sulfonyl sources are involved with dimethyl sulfoxide
(DMSO),10 sodium sulfinate (RSO2Na),11–14 sulfonyl chloride
(RSO2Cl),15 and sulfonyl hydrazide (RSO2HNH2).16 Thus, the
development of a one-pot, open-vessel, and gram-scale
method is highly in demand. In comparison to the above re-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

B
M.-Y. Chang et al.
Paper
Synthesis
Table 1 Reaction Conditionsa
Ar
Ar
O
S
[RSO2] synthon
O
or
R
O
MeO
MeO
MeO
MeO
S
Tol
Ar
promoters, Ac2O
promoters
O
O
Ar
then TolSO2Na (3a)
2a
1a
R1/H
DMSO10
Ar
Entry
Promoters
(equiv)
Solvent
(mL)
Temp
(°C)
Time
(h)
Yield (%)b
of 1a
Ar
+
Cu(I), t-BuOK (Yuan)
Cu(II), HPO(OEt)2 (Chen)
NH4I, H2O (Yuan, Li)
+
Me2SO
Cu(I), O2 (Loh)
Me2SO
c
1
2
PPA (1.0)
PPA 1.0)
PPA 1.0)
PPA (1.0)
PPA (1.0)
–
25
25
25
25
25
25
25
25
25
80
25
25
25
4
90
65
52
40
18
MeNO2 (1)
MeNO2 (2)
MeNO2 (4)
DMAc (4)
4
4
Sulfinates11–14
Pd(II)/Ag(I) (Tan)
Cu(II) (Guo)
CO2H
Mn(III) (Xiang)
K2CO3 (Jiang)
Ar
3
PhI(OAc)2 (Kuhakarn)
I2 (Yuan)
+
4
4
electrolysis (Zha, Wang)
RSO2Na
5
4
c
d
R1/H
6
H2SO4 (1.0)
p-TsOH (1.0)
AcOH (1.0)
H3BO3 (1.0)
PPA (1.0)
–
4
–
Cu(I) (Taniguchi)
Cu(II) (Kumar)
H3PO4 (Zhang)
Pd(II) (Jiang)
c
Cu(I) (Taniguchi)
KI, NaIO4 (Das)
NaI, CAN (Nair)
7
–
4
66
Ar
Ar
+
c
10e
~5e
81
+
8
–
4
RSO2Na
RSO2Na
c
9
–
4
c
10
11
12
13
–
4
Br
+
O
c
Br
B(OH)2
STol
Br
PPA (1.0)
–
10
4
88
Ar
Ar
Ar
Ar
Ar
c
+
PPA (0.5)
–
57
+
+
+
RSO2Na
RSO2Na
RSO2Na
RSO2Na
RSO2Na
c
PPA (0.1)
–
4
12e
a Reactions were run on a 5.0 mmol scale with 2a, Ac2O (1.0 equiv), TolSO2Na
LiBr (Yadav)
DMF (Liang)
HCl (Chen, Yu)
Cu(I) (Ma)
Cu(I) (Fu)
PhI(OAc)2 (Lu, Yi)
(3a; 2.0 equiv).
b Isolated yields.
Cu(II) (Batey, Tse)
c Solvent-free conditions.
d Complex mixture.
e Compound 2a was recovered in major amount.
R1/H
R1/H
Sulfonyl chlorides15
Sulfonyl hydrazides16
Ar
Ar
In(III), NaBH4 (Deng)
Ag(I) (Deng)
+
Cu(I), O2, DMSO (Jiang)
I2, TBHP, DBU (Singh)
eosin Y, light (Weng)
+
RSO2Cl
RSO2NHNH2
nation for the formation of 1a. On the basis of the above op-
timal reaction conditions, the substrate scope and the re-
sults were explored are shown in Table 2. Using different Ar
groups in 2a–p [Ar = a, 3,4-(MeO)2C6H3; b, Ph; c, 4-
MeOC6H4; d, 3-MeOC6H4; e, 4-FC6H4; f, Tol; g, 4-PhC6H4; h,
2-naphthyl; i, 3,4-CH2O2C6H3; j, 3,4-Cl2C6H3; k, 3,4,5-
(MeO)3C6H2; l, 2-furyl; m, 2-thienyl; n, 2-pyridyl; o, Me; p,
2-AcO], and different R groups in 3a–m [Ar = a, Tol, b, Ph; c,
Me; d, n-Bu; e, 4-FC6H4; f, 4-MeOC6H4; g, 3-MeC6H4; h, 4-i-
PrC6H4; i, 4-BuC6H4; j, 4-t-BuC6H4; k, 2-styryl; l, (E)-1-
CH=CH-3,4-(MeO)2C6H3; m, benzyl], products 1a–ac were
synthesized in yields ranging from 41–93%. For Ar and R
substituents, the electron-donating aryl groups, electron-
neutral aryl groups, and electron-withdrawing aryl groups
were well tolerated. Moreover, divinyl sulfones 1k and 1l
could be prepared by the present route.19 Especially, func-
tionalized divinyl sulfones displayed some diverse applica-
tions in synthetic synthons, precursors of polymeric macro-
cycles, and biological molecules (Table 2, entries 11, 12).19c
For the reaction of 2l–n with a heterocyclic ring, 1z was
formed in an 84% yield; however, 1y and 1aa were obtained
in 69% and 41% yield, respectively (entries 25–27). The rea-
son for this could be that the furan ring (for 1y) with lower
aromaticity was more unstable than the thiophene ring (for
Fe(II) (Taniguchi)
Scheme 1 Synthetic routes for β-sulfonyl styrenes
O
then NaSO2R 3
PPA, Ac2O
O
OAc
OAc
S
R
Ar
Ar
Ar
O
2
1
Scheme 2 Our route for β-sulfonyl styrenes
lated yields of the desired 1a decreased slightly to 81% (en-
try 10). Attempts to adjust the time (4 → 10 h) afforded a
similar yield (88%, entry 11). Furthermore, when we de-
creased the equivalent of PPA (1.0 → 0.5 → 0.1), the yields of
1a decreased as well (entries 12, 13).
For the generation β-sulfonyl styrenes 1, we believe that
PPA should be an optimal promoter. With the results in
hand, three Lewis acids (ZnCl2, InCl3, BiCl3)17f were explored
next. Under similar conditions, catalytic amounts (10% mol)
of InCl3 or BiCl3 gave 69% and 76% yield, respectively; how-
ever, there was no reaction for ZnCl2. Regarding a cheaper
promoter, higher yield and activity, we believe that the
PPA/Ac2O combination system should be an optimal combi-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

C
M.-Y. Chang et al.
Paper
Synthesis
1z) in a concentrated solution. Also, the nitrogen atom of
the pyridine ring (for 1aa) could block the proton to form a
pyridinium such that 1a was isolated in a lower yield. Be-
sides the aromatic ring, reaction with 2o with a methyl
substituent (an aliphatic group) was performed (entry 28);
however, 1ab was isolated in only a 67% yield. The reason
could be that 2o has no aryl group so the double bond was
not easy to form in comparison with the Ar group on skele-
ton 2. As shown in Figure 1, the surrogates of ON013100,
1m and 1n with a skeleton of benzyl styryl sulfone, were
synthesized by the gram-scale route. ON013100 has been
reported as a class of non-ATP competitive molecules, and
it is under evaluation as an anticancer agent.20 Moreover,
when the scale for the PPA/Ac2O-mediated reaction of 2a
with 3m was increased to 10 mmol (1.8 g) and 20 mmol
(3.6 g), 1n was isolated in 84% (2.67 g) and 82% (5.22 g)
yield, respectively, under optimal conditions.
OMe
O
S
OMe
O
S
Y
Y
Table 2 Synthesis of 1a
OH
O
O
MeO
OMe
ON013100
O
PPA, Ac2O
O
S
R
1m (Y = H)
Ar
Ar
1n (Y = OMe)
then NaSO2R 3
O
2
1
Figure 1 Structures of ON013100 and 1m,n
Entry 2, Ar
3, R
1 (%)b
On the basis of the above-mentioned experimental re-
sults, a possible reaction mechanism is shown in Scheme 3.
Initially, the intermolecular reaction of 2 with the in situ
formed A (derived from PPA mediated protonation of Ac2O)
generated B via a possible six-membered transition state.
Next, protonated diacetate B was converted into C having
an oxonium ion and AcOH. By the involvement of RSO2Na 3
(2 equiv), D was produced along with the removal of ace-
tate ion and sulfinic acid via the addition of C with one
equivalent of RSO2Na (path a). In another way, the in situ
formed AcOH could react with C to go back into B under the
equilibrium (path b). Subsequently, the released acetate ion
or another equivalent of the sulfinate ion trapped the β-
proton to provide 1 via the elimination pathway. Following
a protonation–deprotonation process, the reaction equation
for ‘AcONa + RSO2H ⇄ AcOH + RSO2Na’ was achieved.
1
2
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2a, 3,4-(MeO)2C6H3
2b, Ph
3a, Tol
1a, 90
1b, 86
1c, 89
1d, 86
1e, 88
1f, 92
1g, 90
1h, 93
1i, 93
3b, Ph
3
3c, Me
4
3d, n-Bu
5
3e, 4-FC6H4
3f, 4-MeOC6H4
3g, 3-MeC6H4
3h, 4-i-PrC6H4
3i, 4-BuC6H4
3j, 4-t-BuC6H4
3k, 2-styryl
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
1j, 90
1k, 80
1l, 86
2a, 3,4-(MeO)2C6H3
2b, Ph
3l, CH=CH-3,4-(MeO)2C6H3
3m, CH2Ph
3m, CH2Ph
3a, Tol
1m, 74
1n, 86
1o, 80
1p, 83
1q, 80
1r, 72
1s, 70
1t, 76
1u, 81
1v, 86
1w, 82
1x, 89
1y, 69
1z, 84
1aa, 41
1ab, 67
1ac, 80
2a, 3,4-(MeO)2C6H3
2b, Ph
O
Me
O
Ar
O
O
Ar
Me
H
2c, 4-MeOC6H4
2d, 3-MeOC6H4
2e, 4-FC6H4
3a, Tol
2
Ar
H
O
O
O
3a, Tol
O
O
+ AcO
Me
PPA, Ac2O
A
3a, Tol
B
Me
2
path b
2f, Tol
3a, Tol
O
S
+ RSO2
AcO
+ RSO2H
AcOH
2g, 4-PhC6H4
3a, Tol
R
2
Me
O
a
2h, 2-naphthyl
2i, 3,4-CH2O2C6H3
2j, 3,4-Cl2C6H3
2k, 3,4,5-(MeO)3C6H2
2l, 2-furyl
3a, Tol
H
O
S
O
S
O
O
R
O
O
R
Ar
H
3a, Tol
β
Ar
Ar
b
path a
O
O
O
O
3a, Tol
D
1
C
Me
3a, Tol
Me
3a, Tol
Scheme 3 Possible mechanism
2m, 2-thienyl
3a, Tol
As an extension for the application of β-sulfonyl sty-
renes 1, the synthesis of sulfonyl 2H-chromene 5 was ex-
plored next, as shown in Scheme 4. Under the Dean–Stark
distillation conditions, treatment of 1a with o-hydroxy-
benzaldehyde (4) provided 5 in a 76% yield via a domino se-
quence of oxa-Michael addition and Knoevengel condensa-
tion. The 2H-chromene skeleton is an important substruc-
2n, 2-pyridyl
3a, Tol
2o, Me
3b, Ph
2p, 2-AcO
3a, Tol
a Reactions were carried out on a 5.0 mmol scale with 2, PPA (490 mg, 1.0
equiv), Ac2O (510 mg, 1.0 equiv), 25 °C, 10 min; then RSO2Na 3 (2.0
equiv), 25 °C, 4 h.
b Isolated yields.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

D
M.-Y. Chang et al.
Paper
Synthesis
O
S
O
Tol
CHO
MeO
MeO
Tol
S
piperidine, AcOH
toluene, reflux
O
O
+
OMe
OMe
OH
O
4
1a
5 (76%)
Scheme 4 Synthesis of 5
ture in a wide range of bioactive heterocycles.21 This
implies that β-sulfonyl styrene 1 is an excellent block for
the formation of sulfonyl 2H-chromene 5.
13C NMR (100 MHz, CDCl3): δ = 151.6, 149.1, 144.0, 141.9, 138.0,
129.8 (2 ×), 127.4 (2 ×), 125.2, 124.9, 123.3, 110.9, 109.7, 55.9, 55.8,
21.5.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C17H19O4S: 319.1004; found:
319.1005.
In summary, we have developed a simple and gram-
scale synthesis of β-sulfonyl styrenes in moderate to good
yields via one-pot PPA-catalyzed 1,1-diacetoxylation of
arylacetaldehydes with acetic anhydride followed by deace-
toxylative sulfonylation of the resulting 1,1-diacetate inter-
mediate with sodium sulfinates under solvent-free condi-
tions. A plausible mechanism has been discussed and pro-
posed. The synthetic extension of β-sulfonyl styrenes in the
preparation of a 2H-chromene skeleton has been included.
Further investigation regarding synthetic applications of
sodium sulfinates will be conducted and published in due
course.
(E)-4-(2-Benzenesulfonylvinyl)-1,2-dimethoxybenzene (1b)22b
Yield: 1.31 g (86%); white solid; mp 149–151 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.93–7.90 (m, 2 H), 7.59 (d, J = 15.2 Hz,
1 H), 7.57–7.54 (m, 1 H), 7.51–7.47 (m, 2 H), 7.05 (dd, J = 2.0, 8.4 Hz,
1 H), 6.95 (d, J = 2.0 Hz, 1 H), 6.82 (d, J = 8.4 Hz, 1 H), 6.75 (d, J = 15.6
Hz, 1 H), 3.85 (s, 3 H), 3.83 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.6, 149.1, 142.4, 140.9, 133.0,
129.1 (2 ×), 127.3 (2 ×), 125.0, 124.4, 123.4, 110.9, 109.7, 55.8, 55.7.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H17O4S: 305.0848; found:
305.0849.
(E)-1,2-Dimethoxy-4-(methylsulfonylvinyl)benzene (1c)
All reagents and solvents were obtained from commercial sources
and used without further purification. Reactions were routinely car-
ried out under an atmosphere of air with magnetic stirring. Products
in organic solvents were dried with anhyd MgSO4 before concentra-
tion in vacuo. Melting points were determined with a SMP3 melting
apparatus. 1H and 13C NMR spectra were recorded on a Varian INOVA-
400 spectrometer operating at 400 and 100 MHz, respectively. Chem-
ical shifts (δ) are reported in parts per million (ppm) and the coupling
constants (J) are given in hertz. High-resolution mass spectra (HRMS)
were measured with a mass spectrometer Finnigan/Thermo Quest
MAT 95XL.
Yield: 1.08 g (89%); white solid; mp 127–128 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 15.6 Hz, 1 H), 7.07 (dd,
J = 2.0, 8.4 Hz, 1 H), 6.99 (d, J = 2.0 Hz, 1 H), 6.85 (d, J = 8.4 Hz, 1 H),
6.79 (d, J = 15.2 Hz, 1 H), 3.88 (s, 3 H), 3.87 (s, 3 H), 3.00 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.8, 149.2, 143.7, 124.8, 123.5,
123.4, 111.0, 109.8, 55.9, 55.8, 43.3.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C11H15O4S: 243.0691; found:
243.0693.
(E)-4-(Butylsulfonylvinyl)-1,2-dimethoxybenzene (1d)
Yield: 1.22 g (86%); viscous gum.
β-Sulfonyl Styrenes 1a–ac; General Procedure
1H NMR (400 MHz, CDCl3): δ = 7.45 (d, J = 15.6 Hz, 1 H), 7.06 (dd,
J = 2.0, 8.4 Hz, 1 H), 6.99 (d, J = 2.0 Hz, 1 H), 6.83 (d, J = 8.0 Hz, 1 H),
6.69 (d, J = 15.2 Hz, 1 H), 3.86 (s, 6 H), 3.02–2.98 (m, 2 H), 1.78–1.70
(m, 2 H), 1.44–1.35 (m, 2 H), 0.88 (t, J = 7.2 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.6, 149.1, 144.4, 124.9, 123.3,
121.9, 110.9, 109.8, 55.80, 55.76, 54.8, 24.4, 21.4, 13.4.
Ac2O (510 mg, 5.0 mmol) was added to a stirred solution of the re-
spective arylacetaldehyde 2 (5.0 mmol) at 25 °C. The reaction mixture
was stirred at 25 °C for 2 min. PPA (490 mg, 5.0 mmol) was added
slowly to the reaction mixture at 25 °C over 3 min. The mixture was
stirred at 25 °C for 5 min. Then, the corresponding sodium sulfinate
RSO2Na 3 (10.0 mmol) was added to the mixture at 25 °C and the
mixture was stirred at 25 °C for 4 h. The residue was diluted with H2O
(20 mL) and the mixture was extracted with CH2Cl2 (3 × 20 mL). The
combined organic layers were washed with aq NaHCO3 (3 × 10 mL),
brine, dried, filtered and evaporated to afford the crude product un-
der reduced pressure. Purification on silica gel (hexanes/EtOAc 8:1 to
4:1) afforded compounds 1a–ac (Table 2).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C14H21O4S: 285.1161; found:
285.1161.
(E)-4-[2-(4-Fluorbenzene)sulfonylvinyl]-1,2-dimethoxybenzene
(1e)
Yield: 1.42 g (88%); white solid; mp 120–122 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.92–7.87 (m, 2 H), 7.56 (d, J = 15.6 Hz,
1 H), 7.17–7.11 (m, 2 H), 7.04 (dd, J = 2.0, 8.4 Hz, 1 H), 6.95 (d, J = 2.0
Hz, 1 H), 6.81 (d, J = 8.4 Hz, 1 H), 6.74 (d, J = 15.2 Hz, 1 H), 3.83 (s, 3 H),
3.81 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 165.2 (d, J = 254.0 Hz), 151.7, 149.1,
142.5, 137.0 (d, J = 3.0 Hz), 130.1 (d, J = 9.8 Hz, 2 ×), 124.8, 124.2,
123.4, 116.3 (d, J = 22.7 Hz, 2 ×), 110.8, 109.7, 55.74, 55.67.
(E)-1,2-Dimethoxy-4-[2-(4-methylbenzene)sulfonylvinyl]benzene
(1a)22a
Yield: 1.43 g (90%); white solid; mp 125–127 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.4 Hz, 2 H), 7.57 (d, J = 15.6
Hz, 1 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.06 (dd, J = 2.0, 8.4 Hz, 1 H), 6.95 (d,
J = 2.0 Hz, 1 H), 6.83 (d, J = 8.4 Hz, 1 H), 6.73 (d, J = 15.2 Hz, 1 H), 3.87
(s, 3 H), 3.85 (s, 3 H), 2.40 (s, 3 H).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

E
M.-Y. Chang et al.
Paper
Synthesis
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H16FO4S: 323.0753; found:
(E)-4-[2-(4-tert-Butylbenzene)sulfonylvinyl]-1,2-dimethoxyben-
323.0752.
zene (1j)
Yield: 1.62 g (90%); viscous gum.
(E)-1,2-Dimethoxy-4-[2-(4-methoxybenzene)sulfonylvinyl]ben-
zene (1f)
1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 8.8 Hz, 2 H), 7.58 (d, J = 15.2
Hz, 1 H), 7.50 (d, J = 8.8 Hz, 2 H), 7.05 (dd, J = 2.0, 8.4 Hz, 1 H), 6.96 (d,
J = 2.0 Hz, 1 H), 6.82 (d, J = 8.4 Hz, 1 H), 6.76 (d, J = 15.6 Hz, 1 H), 3.85
(s, 3 H), 3.83 (s, 3 H), 1.28 (s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 156.9, 151.5, 149.1, 141.9, 137.9,
127.2 (2 ×), 126.1 (2 ×), 125.1, 124.8, 123.3, 110.8, 109.7, 55.8, 55.7,
35.0, 30.9 (3 ×).
Yield: 1.54 g (92%); viscous gum.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.8 Hz, 2 H), 7.51 (d, J = 15.6
Hz, 1 H), 7.02 (dd, J = 2.0, 8.4 Hz, 1 H), 6.95–6.91 (m, 3 H), 6.80 (d,
J = 8.4 Hz, 1 H), 6.73 (d, J = 15.2 Hz, 1 H), 3.83 (s, 3 H), 3.81 (s, 3 H),
3.78 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 163.2, 151.4, 149.0, 141.2, 132.3,
129.4 (2 ×), 125.12, 125.06, 123.1, 114.3 (2 ×), 110.8, 109.6, 55.72,
55.66, 55.4.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C20H25O4S: 361.0474; found:
361.0474.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C17H19O5S: 335.0953; found:
(E)-2-(Vinylbenzenesulfonyl)vinylbenzene (1k)19a
335.0955.
Yield: 1.08 g (80%); viscous gum.
1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 15.6 Hz, 2 H), 7.53–7.48 (m,
4 H), 7.44–7.39 (m, 6 H), 6.86 (d, J = 15.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 143.5 (2 ×), 132.5 (2 ×), 131.3 (2 ×),
129.1 (4 ×), 128.5 (4 ×), 126.3 (2 ×).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H15O2S: 271.0793; found:
(E)-1,2-Dimethoxy-4-[2-(3-methylbenzene)sulfonylvinyl]benzene
(1g)
Yield: 1.43 g (90%); white solid; mp 129–131 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.69–7.67 (m, 2 H), 7.56 (d, J = 15.2 Hz,
1 H), 7.36–7.30 (m, 2 H), 7.03 (dd, J = 2.0, 8.4 Hz, 1 H), 6.96 (d, J = 2.0
Hz, 1 H), 6.79 (d, J = 8.4 Hz, 1 H), 6.77 (d, J = 15.6 Hz, 1 H), 3.81 (s, 3 H),
3.79 (s, 3 H), 2.33 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.4, 148.9, 142.0, 140.6, 139.2,
133.7, 128.9, 127.4, 124.9, 124.5, 124.3, 123.3, 110.7, 109.6, 55.7, 55.6,
21.0.
271.0792.
(E)-1,2-Dimethoxy-4-[2-(3,4-dimethoxybenzene)sulfonylvi-
nyl]benzene (1l)
Yield: 1.68 g (86%); white solid; mp 158–160 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 15.6 Hz, 2 H), 7.08 (dd,
J = 2.0, 8.4 Hz, 2 H), 6.99 (d, J = 1.6 Hz, 2 H), 6.86 (d, J = 8.4 Hz, 2 H),
6.71 (d, J = 15.6 Hz, 2 H), 3.90 (s, 6 H), 3.88 (s, 6 H).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C17H19O4S: 319.1004; found:
319.1005.
13C NMR (100 MHz, CDCl3): δ = 151.7 (2 ×), 149.2 (2 ×), 142.8 (2 ×),
125.4 (2 ×), 124.0 (2 ×), 123.3 (2 ×), 111.0 (2 ×), 109.8 (2 ×), 55.9 (2 ×),
55.8 (2 ×).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C20H23O6S: 391.1215; found:
391.1216.
(E)-4-[2-(4-Isopropylbenzene)sulfonylvinyl]-1,2-dimethoxyben-
zene (1h)
Yield: 1.61 g (93%); viscous gum.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.57 (d, J = 15.2
Hz, 1 H), 7.33 (d, J = 8.4 Hz, 2 H), 7.04 (dd, J = 2.0, 8.0 Hz, 1 H), 6.96 (d,
J = 2.0 Hz, 1 H), 6.81 (d, J = 8.4 Hz, 1 H), 6.75 (d, J = 15.6 Hz, 1 H), 3.84
(s, 3 H), 3.82 (s, 3 H), 2.96–2.89 (m, 1 H), 1.20 (d, J = 7.2 Hz, 6 H).
13C NMR (100 MHz, CDCl3): δ = 154.6, 151.5, 149.0, 141.9, 138.2,
127.5 (2 ×), 127.2 (2 ×), 125.1, 124.8, 123.3, 110.8, 109.7, 55.8, 55.7,
34.0, 23.4 (2 ×).
(E)-2-(Benzylsulfonyl)vinylbenzene (1m)
Yield: 955 mg (74%); white solid; mp 140–142 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.44–7.37 (m, 11 H), 6.71 (d, J = 15.6
Hz, 1 H), 4.32 (s, 2 H).
13C NMR (100 MHz, CDCl3): δ = 145.5, 132.1, 131.3, 130.9 (2 ×), 129.0
(2 ×), 128.83, 128.77 (2 ×), 128.4 (2 ×), 128.0, 123.8, 61.8.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H15O2S: 259.0793; found:
HRMS (ESI-TOF): m/z [M + H]+ calcd for C19H23O4S: 347.1317; found:
347.1320.
259.0795.
(E)-4-[2-(4-Butylbenzene)sulfonylvinyl]-1,2-dimethoxybenzene
(1i)
(E)-4-(2-Benzylsulfonylvinyl)-1,2-dimethoxybenzene (1n)22c
Yield: 1.67 g (93%); viscous gum.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.58 (d, J = 15.6
Hz, 1 H), 7.31 (d, J = 8.4 Hz, 2 H), 7.06 (dd, J = 2.0, 8.4 Hz, 1 H), 6.96 (d,
J = 2.0 Hz, 1 H), 6.83 (d, J = 8.4 Hz, 1 H), 6.74 (d, J = 15.6 Hz, 1 H), 3.87
(s, 3 H), 3.85 (s, 3 H), 2.66 (t, J = 7.6 Hz, 2 H), 1.61–1.53 (m, 2 H), 1.36–
1.27 (m, 2 H), 0.89 (t, J = 7.2 Hz, 3 H).
Yield: 1.37 g (86%); white solid; mp 141–143 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.36–7.34 (m, 5 H), 7.32 (d, J = 15.6 Hz,
1 H), 7.00 (dd, J = 2.0, 8.0 Hz, 1 H), 6.90 (d, J = 2.0 Hz, 1 H), 6.85 (d,
J = 8.4 Hz, 1 H), 6.57 (d, J = 15.2 Hz, 1 H), 4.29 (s, 2 H), 3.90 (s, 3 H),
3.86 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 151.6, 149.1, 148.9, 141.9, 138.1,
129.2 (2 ×), 127.4 (2 ×), 125.2, 124.9, 123.3, 110.9, 109.7, 55.9, 55.8,
35.4, 33.1, 22.1, 13.7.
13C NMR (100 MHz, CDCl3): δ = 151.8, 149.2, 145.5, 130.9 (2 ×), 128.8
(2 ×), 128.7, 128.2, 125.0, 123.2, 121.2, 111.0, 110.0, 61.9, 55.93,
55.87.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C20H25O4S: 361.0474; found:
HRMS (ESI-TOF): m/z [M + H]+ calcd for C17H19O4S: 319.1004; found:
361.0474.
319.1003.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

F
M.-Y. Chang et al.
Paper
Synthesis
(E)-2-[(4-Methylbenzene)sulfonylvinyl]benzene (1o)11g
(E)-3-[2-(4-Methylbenzene)sulfonylvinyl]-1-phenylbenzene (1t)
Yield: 1.03 g (80%); white solid; mp 119–121 °C (hexanes/EtOAc).
Yield: 1.27 g (76%); white solid; mp 225–226 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.65 (d, J = 15.2
Hz, 1 H), 7.48–7.45 (m, 2 H), 7.40–7.37 (m, 3 H), 7.33 (d, J = 8.4 Hz, 2
H), 6.85 (d, J = 15.2 Hz, 1 H), 2.42 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 7.85 (d, J = 8.4 Hz, 2 H), 7.69 (d, J = 15.6
Hz, 1 H), 7.63–7.54 (m, 6 H), 7.47–7.43 (m, 2 H), 7.40–7.34 (m, 3 H),
6.70 (d, J = 15.2 Hz, 1 H), 2.44 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.32, 141.85, 137.70, 132.38,
131.03, 129.90 (2 ×), 128.99 (2 ×), 128.44 (2 ×), 127.63 (2 ×), 127.59,
21.53.
13C NMR (100 MHz, CDCl3): δ = 144.4, 143.9, 141.5, 139.8, 137.8,
131.4, 130.0 (2 ×), 129.0 (2 ×), 128.9 (2 ×), 128.1, 127.7 (2 ×), 127.7 (2
×), 127.3, 127.0 (2 ×), 21.6.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H15O2S: 259.0793; found:
HRMS (ESI-TOF): m/z [M + H]+ calcd for C21H19O2S: 335.1106; found:
259.0795.
335.1106.
(E)-1-Methoxy-4-[2-(4-methylbenzene)sulfonylvinyl]benzene
(E)-2-[2-(4-methylbenzene)sulfonylvinyl]naphthalene (1u)22e
(1p)22d
Yield: 1.25 g (81%); white solid; mp 126–128 °C (hexanes/EtOAc).
Yield: 1.20 g (83%); white solid; mp 81–83 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.93 (s, 1 H), 7.88–7.80 (m, 6 H), 7.56–
7.50 (m, 3 H), 7.35 (d, J = 7.6 Hz, 2 H), 6.96 (d, J = 15.2 Hz, 1 H), 2.44 (s,
3 H).
13C NMR (100 MHz, CDCl3): δ = 144.4, 142.0, 137.8, 134.4, 133.1,
130.8, 130.0 (2 ×), 129.9, 128.9, 128.6, 127.8, 127.7 (3 ×), 127.6, 126.9,
123.4, 21.6.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.4 Hz, 2 H), 7.59 (d, J = 15.2
Hz, 1 H), 7.41 (d, J = 8.8 Hz, 2 H), 7.31 (d, J = 8.4 Hz, 2 H), 6.88 (d, J = 8.8
Hz, 2 H), 6.70 (d, J = 15.6 Hz, 1 H), 3.81 (s, 3 H), 2.41 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 161.9, 144.0, 141.6, 138.1, 130.2 (2 ×),
129.8 (2 ×), 127.4 (2 ×), 124.9, 124.7, 114.4 (2 ×), 55.3, 21.5.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H17O3S: 289.0898; found:
HRMS (ESI-TOF): m/z [M + H]+ calcd for C19H17O2S: 309.0949; found:
289.0899.
309.0950.
(E)-1-Methoxy-3-[2-(4-methylbenzene)sulfonylvinyl]benzene
(E)-1,2-Dimethylenedioxy-4-[2-(4-methylbenzene)sulfonylvi-
nyl]benzene (1v)
(1q)22d
Yield: 1.15 g (80%); white solid; mp 53–55 °C (hexanes/EtOAc).
Yield: 1.30 g (86%); white solid; mp 112–113 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.61 (d, J = 15.6
Hz, 1 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.27 (t, J = 8.0 Hz, 1 H), 7.05 (d, J = 8.0
Hz, 1 H), 6.97 (t, J = 1.6 Hz, 1 H), 6.93 (dt, J = 1.6, 8.4 Hz, 1 H), 6.67 (d,
J = 15.2 Hz, 1 H), 3.78 (s, 3 H), 2.41 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.4 Hz, 2 H), 7.54 (d, J = 15.2
Hz, 1 H), 7.33 (d, J = 8.4 Hz, 2 H), 6.98 (dd, J = 1.6, 8.0 Hz, 1 H), 6.92 (d,
J = 2.0 Hz, 1 H), 6.80 (d, J = 8.0 Hz, 1 H), 6.65 (d, J = 15.2 Hz, 1 H), 5.99
(s, 2 H), 2.42 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 159.8, 144.3, 141.7, 137.6, 133.6,
13C NMR (100 MHz, CDCl3): δ = 150.2, 148.4, 144.2, 141.7, 138.0,
129.94, 129.85 (2 ×), 127.8, 127.6 (2 ×), 121.0, 116.9, 113.2, 55.2, 21.5.
129.9 (2 ×), 127.5 (2 ×), 126.7, 125.3, 125.2, 108.6, 106.8, 101.7, 21.5.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H17O3S: 289.0898; found:
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H15O4S: 303.0691; found:
289.0897.
303.0693.
(E)-1-Fluoro-3-[2-(4-methylbenzene)sulfonylvinyl]benzene (1r)22d
(E)-1,2-Dichloro-4-[2-(4-methylbenzene)sulfonylvinyl]benzene
(1w)
Yield: 994 mg (72%); white solid; mp 86–88 °C (hexanes/EtOAc).
Yield: 1.34 g (82%); white solid; mp 166–167 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.0 Hz, 2 H), 7.61 (d, J = 15.2
Hz, 1 H), 7.49–7.44 (m, 2 H), 7.33 (d, J = 8.4 Hz, 2 H), 7.09–7.04 (m, 2
H), 6.79 (d, J = 15.6 Hz, 1 H), 2.42 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 164.2 (d, J = 251.7 Hz), 144.4, 140.5,
137.6, 130.5 (d, J = 8.4 Hz, 2 ×), 1299 (2 ×), 128.7 (d, J = 3.1 Hz), 127.6
(2 ×), 127.4 (d, J = 2.3 Hz), 116.2 (d, J = 22.0 Hz, 2 ×), 21.5.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.4 Hz, 2 H), 7.55 (d, J = 2.4
Hz, 1 H), 7.54 (d, J = 15.2 Hz, 1 H), 7.46 (d, J = 8.4 Hz, 1 H), 7.35 (d,
J = 8.4 Hz, 2 H), 7.29 (dd, J = 2.4, 8.4 Hz, 1 H), 6.85 (d, J = 15.2 Hz, 1 H),
2.44 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.8, 139.0, 137.1, 135.1, 133.5,
132.4, 131.0, 130.1 (2 ×), 129.9, 129.6, 127.8 (2 ×), 127.5, 21.6.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H13Cl2O2S: 327.0013;
HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H14FO2S: 277.0699; found:
277.0697.
found: 327.0015.
(E)-1-Methyl-3-[2-(4-methylbenzene)sulfonylvinyl]benzene
(1s)22d
(E)-1,2,3-Trimethoxy-5-[2-(4-methylbenzene)sulfonylvinyl]ben-
zene (1x)
Yield: 952 mg (70%); white solid; mp 149–151 °C (hexanes/EtOAc).
Yield: 1.55 g (89%); white solid; mp 107–109 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.62 (d, J = 15.6
Hz, 1 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.18 (d, J = 8.0
Hz, 2 H), 6.79 (d, J = 15.2 Hz, 1 H), 2.42 (s, 3 H), 2.36 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.2, 141.9, 141.7, 137.9, 129.9 (2 ×),
129.7 (2 ×), 129.6, 128.5 (2 ×), 127.6 (2 ×), 126.4, 21.5, 21.4.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.0 Hz, 2 H), 7.56 (d, J = 15.2
Hz, 1 H), 7.31 (d, J = 8.0 Hz, 2 H), 6.79 (d, J = 15.2 Hz, 1 H), 6.70 (s, 2 H),
3.84 (s, 3 H), 3.83 (s, 6 H), 2.40 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 153.4 (2 ×), 144.2, 141.9, 140.6, 137.8,
129.9 (2 ×), 127.7, 127.5 (2 ×), 126.6, 105.7 (2 ×), 60.8, 56.1 (2 ×), 21.5.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C18H21O5S: 349.1110; found:
HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H17O2S: 273.0949; found:
273.0951.
349.1112.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

G
M.-Y. Chang et al.
Paper
Synthesis
(E)-2-[4-Methylbenzene)sulfonylvinyl]furan (1y)22f
2-(3,4-Dimethoxyphenyl)-3-(toluene-4-sulfonyl)-2H-chromene
(5)
Yield: 856 mg (69%); white solid; mp 96–98 °C (hexanes/EtOAc).
Piperidine (51 mg, 0.6 mmol) and AcOH (54 mg, 0.9 mmol) were add-
ed to a solution of 1a (1.0 mmol) in toluene at r.t. The reaction mix-
ture was stirred at r.t. for 10 min. The mixture was stirred at reflux for
10 h using the Dean–Stark distillation apparatus. The mixture was
cooled to r.t. and the solvent was evaporated. The residue was diluted
with H2O (10 mL) and the mixture was extracted with CH2Cl2 (3 × 20
mL). The combined organic layers were washed with brine, dried, fil-
tered, and evaporated under reduced pressure to afford the crude
product. Purification on silica gel (hexanes/EtOAc 8:1 to 3:1) afforded
5; yield: 242 mg (76%); colorless gum.
1H NMR (400 MHz, CDCl3): δ = 7.74 (s, 1 H), 7.54 (d, J = 8.4 Hz, 2 H),
7.23 (dt, J = 1.6, 7.6 Hz, 1 H), 7.19 (dd, J = 1.6, 8.0 Hz, 1 H), 7.13 (d,
J = 8.4 Hz, 2 H), 6.92 (dt, J = 1.6, 7.6 Hz, 1 H), 6.74 (dd, J = 2.0, 8.4 Hz,
1 H), 6.72 (d, J = 8.4 Hz, 1 H), 6.67 (d, J = 2.0 Hz, 1 H), 6.58 (d, J = 8.4 Hz,
1 H), 6.07 (s, 1 H), 3.79 (s, 3 H), 3.67 (s, 3 H), 2.35 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 8.4 Hz, 2 H), 7.44 (d, J = 1.6
Hz, 1 H), 7.39 (d, J = 15.2 Hz, 1 H), 7.30 (d, J = 8.4 Hz, 2 H), 6.71 (d,
J = 15.2 Hz, 1 H), 6.67 (d, J = 3.2 Hz, 1 H), 6.45 (dd, J = 1.6, 3.2 Hz, 1 H),
2.34 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 148.6, 145.5, 144.2, 137.8, 129.8 (2 ×),
128.3, 127.4 (2 ×), 125.0, 116.6, 112.5, 21.5.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C13H13O3S: 249.0586; found:
249.0587.
(E)-2-(4-Methylbenzene)sulfonylvinyl)thiophene (1z)22f
Yield: 1.11 g (84%); white solid; mp 131–132 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.4 Hz, 2 H), 7.75 (d, J = 14.8
Hz, 1 H), 7.41 (d, J = 4.8 Hz, 1 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.28 (d, J = 3.6
Hz, 1 H), 7.04 (dd, J = 3.6, 4.8 Hz, 1 H), 6.63 (d, J = 14.8 Hz, 1 H), 2.31 (s,
3 H).
13C NMR (100 MHz, CDCl3): δ = 144.3, 137.8, 136.9, 134.5, 132.2,
129.9 (2 ×), 129.8, 128.2, 127.5 (2 ×), 125.7, 21.5.
13C NMR (100 MHz, CDCl3): δ = 152.5, 149.6, 148.7, 144.3, 136.8,
134.0, 133.0, 132.9, 129.5 (2 ×), 129.1, 129.0, 127.9 (2 ×), 121.9, 120.7,
119.5, 117.0, 110.7, 110.5, 74.9, 55.8, 55.6, 21.5.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C24H23O5S: 423.1266; found:
423.1267.
HRMS (ESI-TOF): m/z [M + H]+ calcd for C13H13O2S2: 265.0357; found:
265.0358.
(E)-2-[(4-Methylbenzene)sulfonylvinyl]pyridine (1aa)22f
Funding Information
Yield: 531 mg (41%); white solid; mp 90–92 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 8.57 (br d, J = 8.8 Hz, 1 H), 7.81 (d,
J = 8.4 Hz, 2 H), 7.70 (dt, J = 1.6, 7.6 Hz, 1 H), 7.59 (d, J = 14.8 Hz, 1 H),
7.41 (d, J = 14.8 Hz, 1 H), 7.37 (d, J = 7.6 Hz, 1 H), 7.30 (d, J = 8.0 Hz, 2
H), 7.25 (ddd, J = 0.8, 4.4, 8.4 Hz, 1 H), 2.39 (s, 3 H).
The authors would like to thank the Ministry of Science and Technol-
ogy of the Republic of China for the financial support (MOST 106-
2628-M-037-001-MY3).
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13C NMR (100 MHz, CDCl3): δ = 150.9, 150.1, 144.5, 140.0, 137.1,
137.0, 132.0, 129.9 (2 ×), 127.8 (2 ×), 125.3, 124.8, 21.5.
Supporting Information
HRMS (ESI-TOF): m/z [M + H]+ calcd for C14H14NO2S: 260.0745; found:
260.0746.
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-xxxxxxx.
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
ortioInfgrmoaitn
(E)-1-(Benzenesulfonylvinyl)prop-1-ene (1ab)
References
Yield: 610 mg (67%); white solid; mp 58–60 °C (hexanes/EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.71–7.68 (m, 2 H), 7.43–7.38 (m, 1 H),
7.38–7.32 (m, 2 H), 6.78 (dq, J = 6.8, 14.0 Hz, 1 H), 6.22 (dq, J = 1.6,
14.0 Hz, 1 H), 1.69 (dd, J = 1.2, 7.2 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 142.2, 140.1, 132.7, 131.1, 128.7 (2 ×),
126.8 (2 ×), 16.6.
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HRMS (ESI-TOF): m/z [M + H]+ calcd for C9H11O2S: 183.0480; found:
183.0481.
Acetic Acid 2-[2-(Toluene-4-sulfonyl)vinyl]phenyl Ester (1ac)
Yield: 1.26 g (80%); viscous gum.
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.4 Hz, 2 H), 7.70 (d, J = 15.6
Hz, 1 H), 7.51 (dd, J = 2.0, 8.0 Hz, 1 H), 7.42 (dt, J = 2.0, 8.4 Hz, 1 H),
7.34 (d, J = 8.4 Hz, 2 H), 7.23 (dt, J = 1.2, 8.4 Hz, 1 H), 7.14 (dd, J = 1.2,
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317.0850.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H

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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–H