PhI(OAc)2 mediated decarboxylative sulfonylation of β-aryl-α,β-unsaturated carboxylic acids: A synthesis of (E)-vinyl sulfones

Article abstract of DOI:10.1039/c5ob00417a

A highly efficient metal-free decarboxylative sulfonylation protocol for the preparation of (E)-vinyl sulfones from of β-aryl-α,β-unsaturated carboxylic acids using sodium sulfinates and (diacetoxyiodo)benzene (PhI(OAc)₂) was developed. This strategy offers a simple and expedient synthesis of (E)-vinyl sulfones bearing a wide variety of functional groups. A radical-based pathway has been proposed for this decarboxylative sulfonylation reaction.

Full text of DOI:10.1039/c5ob00417a

Organic &
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PhI(OAc)2 mediated decarboxylative sulfonylation
of β-aryl-α,β-unsaturated carboxylic acids:
a synthesis of (E)-vinyl sulfones†
Cite this: Org. Biomol. Chem., 2015,
13, 4785
Praewpan Katrun,a Sornsiri Hlekhlai,a Jatuporn Meesin,a Manat Pohmakotr,a
Vichai Reutrakul,a Thaworn Jaipetch,b Darunee Soorukrama and
Chutima Kuhakarn*a
A highly efficient metal-free decarboxylative sulfonylation protocol for the preparation of (E)-vinyl
sulfones from of β-aryl-α,β-unsaturated carboxylic acids using sodium sulfinates and (diacetoxyiodo)-
benzene (PhI(OAc)2) was developed. This strategy offers a simple and expedient synthesis of (E)-vinyl
sulfones bearing a wide variety of functional groups. A radical-based pathway has been proposed for this
decarboxylative sulfonylation reaction.
Received 3rd March 2015,
Accepted 17th March 2015
DOI: 10.1039/c5ob00417a
www.rsc.org/obc
benzene (PhI(OAc)2, DIB), a commercially available iodine(III)
reagent, has received much interest and its synthetic utility as
Introduction
Decarboxylation accompanied by a simultaneous functionali- an efficient oxidative functionalization reagent has been
zation reaction has emerged as a synthetically important trans- demonstrated by several groups.4 Our research group has long
formation in current organic synthesis, leading to carbon– been interested in the functionalization of alkenes and alkynes
carbon and carbon–heteroatom bond formation. Aromatic, promoted by hypervalent iodine compounds including iodoxy-
α,β-unsaturated, alkynyl as well as aliphatic carboxylic acids benzoic acid (IBX) and DIB.5 In this context, we report herein
can be used as substrates to yield numerous more highly func- our research results on the decarboxylative sulfonylation of
tionalized compounds.1
unsaturated carboxylic acids mediated by (diacetoxyiodo)
Vinyl sulfones are particularly valuable units in organic syn- benzene (DIB). Our method offers several advantages, includ-
thesis due to chemical versatility of the sulfonyl moiety which ing being transition-metal-free, employing environmentally
can be further manipulated into other useful functional benign and stable reagents, and involving simple handling
groups. A vast number of synthetic routes are available toward under air-stable conditions.
the synthesis of vinyl sulfones.2 Very recently, a few approaches
were described for converting α,β-unsaturated carboxylic acids
to vinyl sulfones and 2-sulfonylbenzofuran employing metal-
Results and discussion
catalyzed reactions.3 Although the reported methods employ-
ing transition metal reagents are highly efficient, they require We began our study employing (E)-cinnamic acid (1a) and
complex reaction conditions and long reaction times to facili- sodium benzenesulfinate (2a) as benchmark substrates to
tate product formation.
screen for optimum reaction conditions. A variety of reaction
Hypervalent iodine reagents are widely employed in a parameters including reagent stoichiometry, additive and
variety of chemical transformations and their chemistry solvent were screened and the results are summarized in
has become an area of growing interest due to their benign Table 1. When (E)-cinnamic acid (1a, 1 equiv.) was treated with
properties, selectivity and ease of handling. (Diacetoxyiodo)- sodium benzenesulfinate (2a, 1 equiv.) in the presence of DIB
(1 equiv.) under air in N,N-dimethylformamide (DMF) as
solvent at 100 °C for 1 h, (E)-(2-(phenylsulfonyl)vinyl)benzene
aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry
(PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400,
Thailand. E-mail: chutima.kon@mahidol.ac.th
bMahidol University and Center of Excellence for Innovation in Chemistry
(PERCH-CIC), Kanchanaburi Campus, Saiyok, Kanchanaburi 71150, Thailand
†Electronic supplementary information (ESI) available. See DOI: 10.1039/
c5ob00417a
(3a) was isolated in 17% yield (Table 1, entry 1). In order to
improve the reaction yield, an excess quantity of DIB (2 equiv.)
was employed (Table 1, entry 2). Unfortunately, no appreciable
improvement was obtained. Increasing the stoichiometry of 2a
from 1 equivalent to 2–4 equivalents dramatically improved the
yields of 3a from 20% yield to 70% yield (Table 1, entries 3–5).
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Table 1 Optimization of the reaction conditionsa
with cinnamic acid derivatives containing electron-donating
substituents on the phenyl ring (4-N(CH3)2, 4-CH3, 2-OH,
3-OH, 4-OH, 3-OCH3, 4-OCH3, 2,3-(OCH3)2, 2,5-(OCH3)2, 3,4-
OCH2O, 2,4,5-(OCH3)3, and 3,4,5-(OCH3)3) yielding the respect-
ive products 3h–s in 46–68% yields (Table 2, entries 8–19). (E)-
3-(4-(Allyloxy)phenyl)acrylic acid reacted solely at the unsatu-
rated carboxylic acid moiety to yield 3t in 45% yield (Table 2,
entry 20). Even though longer reaction times (15–30 minutes)
were required for some substrates, it is evident that the
2a
(equiv.)
PhI(OAc)2
(equiv.)
Time
(h)
Yieldb
(%)
Entry
Solvent
1
2
3
4
5
6
7
1
1
2
3
4
4
4
4
4
4
4
4
4
4
4
4
1
2
2
2
2
1
3
2
2
2
2
2
2
2
2
2
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
DMA
DMF
DMF
DMF
DMF
1
1
1
1
1
1
1
1
17
20
37
60
70
45
72
64
58
73
52
66
60
18
69
59
method was compatible with
a variety of electronically
different substituents and with different steric environments
on the phenyl ring of the cinnamic acid derivatives. The reac-
tions of 2a with (E)-3-(naphthalene-2-yl)acrylic acid and
(2E,4E)-5-phenylpenta-2,4-dienoic acid were examined and
gave the corresponding products 3u and 3v in 67% and 50%
yields, respectively (Table 2, entries 21–22). It is also worth
emphasizing that in all cases the vinyl sulfones 3a–v were
obtained as the E configuration. While (E)-3-phenylbut-2-enoic
acid readily reacted with 2a to yield the corresponding (E)-vinyl
sulfone 3w (44% yield) along with allyl sulfone 4w (5% yield)
as a minor product (Table 2, entry 23), (E)-2-methyl-3-phenyl-
acrylic acid was found incompatible even with a prolonged
reaction time (1 h). The reaction was also suitable for hetero-
aromatic-substituted acrylic acids; the reactions of (E)-3-
(pyridin-3-yl)acrylic acid, (E)-3-(pyridin-2-yl)acrylic acid, (E)-3-
(furan-2-yl)acrylic acid, (E)-3-(thiophen-2-yl)acrylic acid, and
(E)-3-(2-pyrrolyl)acrylic acid provided the corresponding pro-
ducts in low to moderate yields (38–66% yields) (Table 2,
entries 24–28). Next the reactions of cinnamic acid (1a) with a
8c
9d
10
11
12
13e
14f
15g
16h
1
10 min
10 min
10 min
1
1
1
10 min
a Reaction conditions: 1a (0.25 mmol) in solvent (3 mL), 100 °C, open
air. b Isolated yield after column chromatography (SiO2). c Reaction was
carried out at room temperature. d Reaction was carried out at
refluxing temperature. e Reaction was carried out employing KI
(1 equiv.) as an additive. f Reaction was carried out employing I2
(1 equiv.) as an additive. g Reaction was carried out employing K2CO3
(1 equiv.) as an additive. h Reaction was carried out under Ar.
While lowering the amount of DIB from 2 equivalents to 1 collection of sodium sulfinates were examined (Table 2,
equivalent drastically reduced the yield of 3a from 70% yield to entries 29–32). Sodium benzenesulfinates bearing electroni-
45% yield, increasing the amount of DIB from 2 equivalents to cally different substituents on the para position (4-CH3, 4-Cl,
3 equivalents did not show significantly higher yield (Table 1, and 4-OCH3) gave comparable results to those of the parent
entries 6–7). Lowering or elevating reaction temperature sodium benzenesulfinate (Table 2, entry 1 vs. entries 29–31).
resulted in slightly lower yields (Table 1, entries 8–9). Much to Although affording 3ad in low yield (24% yield), the reaction
our delight, it is pleasing to find that the reaction was excep- with sodium methanesulfinate was found to be feasible under
tionally rapid and 3a was isolated in 73% yield when the reac- the reaction conditions (Table 2, entry 32). Unfortunately, the
tion was carried out within 10 minutes (Table 1, entry 10). A present protocol is not applicable to β-alkyl-α,β-unsaturated
few solvents were screened including dimethyl sulfoxide carboxylic acid; (E)-2-butenoic acid failed to give any desired
(DMSO) and N,N-dimethylacetamide (DMA) and DMF exhibi- vinyl sulfone product.
ted the optimal results (Table 1, entries 11–12). The presence
To help to better understand the reaction pathway, some
of additives, including KI, I2 and K2CO3 did not help enhan- control experiments were explored. The reaction of (E)-cin-
cing the product yield (Table 1, entries 13–15).5a,7,3b Finally, namic acid (1a) with sodium benzenesulfinate (2a) was carried
the reaction performed under inert atmosphere (argon) gave out under the standard reaction conditions in the presence of
poorer results (Table 1, entry 16). Based on the experimental radical inhibitors, including 2,6-di-tert-butyl-4-methylphenol
results shown in Table 1, the optimized reaction conditions (BHT), 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), and
were chosen as follows: substrate (1 equiv.), sodium sulfinate hydroquinone (Scheme 1a). BHT was found to suppress the
(4 equiv.), DIB (2 equiv.) in DMF at 100 °C (Table 1, entry 10).
reaction while TEMPO and hydroquinone totally stopped the
With the optimized reaction conditions in hand, the sub- reaction. The observed results implied that the reaction prob-
strate scope and limitation of the method were evaluated and ably proceeded via a radical pathway. Next, when styrene was
the results are summarized in Table 2. First the reactions of employed as a substrate in place of (E)-cinnamic acid (1a), only
sodium benzenesulfinate (2a) with cinnamic acid derivatives a trace amount of 3a was observed (TLC analysis). These
were investigated. Those bearing electron-withdrawing substi- results suggested that styrene is not an intermediate in the
tuents on the phenyl ring (4-F, 3-Cl, 2-Br, 4-Br, 4-NO2, and present transformation (Scheme 1b). The product 3a was not
3-CF3) afforded the corresponding products 3b–g in 43–72% observed when ethyl cinnamate was employed as a substrate
yields (Table 2, entries 2–7). Comparable results were observed and almost all of the ethyl cinnamate was recovered (93%
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a
Table 2 Decarboxylative sulfonylation of β-aryl-α,β-unsaturated carboxylic acids mediated by PhI(OAc)2
Time
(min)
Yieldb
(%)
Time
(min)
Yieldb
(%)
Entry
1
Product
Entry
17
Product
10
3a, 73
15
3q, 53
2
3
10
3b, 72
18
19
30
3r, 52
10
3c, 59
30
3s, 59
4
5
6
10
10
30
3d, 61
3e, 69
3f, 43
20
21
22
10
10
10
3t, 45
3u, 67
3v, 50
7
8
10
30
3g, 63
3h, 46
23
24
10
10
3w, 44c
3x, 66
9
15
15
15
3i, 58
3j, 64
3k, 57
25
26
27
10
10
10
3y, 61
3z, 52
3za, 54
10
11
12
13
15
15
3l, 47
28
29
30
10
3zb, 38
3aa, 79
3m, 68
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Table 2 (Contd.)
Time
(min)
Yieldb
(%)
Time
(min)
Yieldb
(%)
Entry
14
Product
Entry
30
Product
15
3n, 50
10
3ab, 71
15
16
15
3o, 64
31
32
10
3ac, 80
15
3p, 65
30
3ad, 24
a Reaction conditions: substrate 1 (0.25 mmol), sodium sulfinate (4 equiv.), PhI(OAc)2 (2 equiv.) in DMF (3 mL), 100 °C, open air. b Isolated yield
after column chromatography (SiO2). c Allyl sulfone 4w was isolated as a minor product (5% yield).
Scheme 2 Possible reaction mechanism.
On the basis of the control experiments mentioned above
and the previously reported literature, a possible reaction
pathway for the decarboxylative sulfonylation of β-aryl-α,β-un-
saturated carboxylic acids mediated by PhI(OAc)2 was deduced
as shown in Scheme 2. Ligand exchange between PhI(OAc)2
and β-aryl-α,β-unsaturated carboxylic acid 1 leads to the for-
mation of intermediate A.7 Next, the sulfonyl radical generated
in situ by the reaction of sodium sulfinate and PhI(OAc)2
attacked the intermediate A at the α-carbon to furnish benzylic
radical intermediate C. Subsequently, the intermediate C
undergoes decarboxylation and PhI loss to provide the vinyl
Scheme 1 Control experiments.
yield) (Scheme 1c). Finally, sodium sulfinate is essential for sulfone product 3 (Scheme 2). The validity of the intermediate
the reaction to proceed efficiently since the reaction of (E)-cin- A possibly formed in the reaction was proved by separate
namic acid (1a) with benzenesulfinic acid under the standard preparation of iodosobenzene dicinnamate 5.7a Treatment of
reaction conditions did not afford the expected product 3a iodosobenzene dicinnamate 5 with sodium benzenesulfinate
(Scheme 1d).
(2a, 4 equiv.) in the presence of DIB (1 equiv.) in DMF at
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Emmons reaction. Purification of the reaction products
was carried out by column chromatography on silica gel
(0.063–0.200 mm). After column chromatography, analytically
pure solid was obtained by crystallization from CH2Cl2–
hexanes.
Scheme 3 Reaction of iodosobenzene dicinnamate
benzenesulfinate (2a).
5 with sodium
General procedure: synthesis of vinyl sulfone from β-aryl-
α,β-unsaturated carboxylic acid and sodium sulfinate. DIB
(161.1 mg, 0.50 mmol) was added to a solution of β-aryl-α,β-
unsaturated carboxylic acid (0.25 mmol) and sodium sulfinate
(1.0 mmol) in DMF (3 mL) at room temperature and then the
reaction mixture was stirred at 100 °C under air for
10–30 minutes. After completion of the reaction, the reaction
was cooled to room temperature and was diluted with water
(10 mL). Further stirring was followed by extraction with EtOAc
(2 × 20 mL). The combined organic extracts were washed with
H2O (20 mL) and brine (20 mL), dried (MgSO4), filtered, and
concentrated (aspirator). The residue was purified by column
chromatography using EtOAc–hexanes as eluent to afford the
corresponding product.
100 °C for 1 h furnished the desired product 3n in 39% yield.
Therefore, the observed results implied that the intermediate
A might be involved as an early intermediate formed in this
reaction (Scheme 3). Additionally, the stability of the radical
intermediate C is highly crucial since the reaction of 2a with
(E)-2-butenoic acid did not furnish the expected vinyl sulfone
product.
Conclusions
(E)-(2-(Phenylsulfonyl)vinyl)benzene (3a).3d Colorless solid,
mp 62–63 °C (CH2Cl2–hexanes); Rf = 0.43 (1 : 3 EtOAc–
hexanes); IR (neat): ν 3044, 2918, 1611, 1574, 1446, 1298, 1142,
In summary, we have developed a facile and expedient protocol
for the formation of (E)-vinyl sulfones from β-aryl-α,β-
unsaturated carboxylic acids and sodium sulfinates through a
PhI(OAc)2 mediated decarboxylative sulfonylation strategy. The
reaction exhibits good substrate scope. A wide range of func-
tionalities both in the unsaturated carboxylic acids and the
sodium sulfinates are tolerated under the reaction conditions.
The method offers an alternative facile synthetic route to (E)-
vinyl sulfones which are valuable scaffolds found in biologi-
cally active substances and important synthetic intermediates.
A preliminary study on the reaction mechanism also implies
that the reaction is probably proceeding through a radical
pathway. To the best of our knowledge, this is the first report
of decarboxylative sulfonylation of δ-aryl-α,β-γ,δ-diene car-
boxylic acids.
1
1084 cm−1; H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 8.8 Hz,
2H), 7.67 (d, J = 15.4 Hz, 1H), 7.60 (t, J = 7.4 Hz, 1H), 7.55–7.51
(m, 2H), 7.47–7.45 (m, 2H), 7.39–7.34 (m, 3H), 6.85 (d, J =
15.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 142.4 (CH), 140.7
(C), 133.3 (CH), 132.3 (C), 131.2 (CH), 129.3 (2 × CH), 129.0
(2 × CH), 128.5 (2 × CH), 127.6 (2 × CH), 127.3 (CH); HRMS m/z
(ESI): calcd for [C14H12O2S + Na]+: 267.0456, found 267.0455.
(E)-1-Fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (3b).3d Color-
less solid, mp 92–93 °C (CH2Cl2–hexanes); Rf = 0.41 (1 : 3
EtOAc–hexanes); IR (neat): ν 3048, 1613, 1599, 1509, 1446,
1302, 1280, 1230, 1141, 1082 cm−1; 1H NMR (400 MHz, CDCl3):
δ 7.93 (d, J = 8.6 Hz, 2H), 7.65–7.59 (m, 2H), 7.54 (t, J = 7.8 Hz,
2H), 7.48–7.45 (m, 2H), 7.07 (t, J = 8.6 Hz, 2H), 6.77 (d, J =
15.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 164.3 (d, J =
251.5 Hz, C), 141.1 (CH), 140.6 (C), 133.4 (CH), 130.6 (d, J =
8.7 Hz, 2 × CH), 129.3 (2 × CH), 128.6 (d, J = 3.3 Hz, C), 127.6
(2 × CH), 127.0 (d, J = 1.9 Hz, CH), 116.3 (d, J = 21.9 Hz,
Experimental
General information
All isolated compounds were characterized on the basis of 2 × CH); HRMS m/z (ESI): calcd for [C14H11FO2S + Na]+:
1H NMR and 13C NMR spectroscopic data, IR spectra, and HRMS 285.0361, found 285.0360.
data. 1H NMR and 13C NMR spectra were recorded on a Bruker
(E)-1-Chloro-3-(2-(phenylsulfonyl)vinyl)benzene (3c).6 Color-
Ascend™ spectrometer. 1H NMR and 13C NMR chemical shifts less solid, mp 83–84 °C (CH2Cl2–hexanes); Rf = 0.43 (1 : 3
are reported in ppm using tetramethylsilane (TMS) as an EtOAc–hexanes); IR (neat): ν 3048, 2919, 2850, 1617, 1562,
internal standard or residual nondeuterated solvent peak as an 1446, 1318, 1142, 1084 cm−1 1H NMR (400 MHz, CDCl3):
;
internal standard. Infrared spectra were recorded with a δ 7.93 (d, J = 8.6 Hz, 2H), 7.64–7.53 (m, 4H), 7.45 (s, 1H),
Bruker ALPHA FT-IR spectrometer. High-resolution mass 7.38–7.29 (m, 3H), 6.86 (d, J = 15.4 Hz, 1H); 13C NMR
spectra (HRMS) were recorded with a Bruker micro TOF (100 MHz, CDCl3): δ 140.7 (CH), 140.3 (C), 135.1 (C), 134.1 (C),
spectrometer in the ESI mode. Melting points were recorded 133.6 (CH), 131.1 (CH), 130.3 (CH), 129.4 (2 × CH), 128.9 (CH),
with a Sanyo Gallenkamp apparatus. Reactions were monitored 128.2 (CH), 127.7 (2 × CH), 126.8 (CH); HRMS m/z (ESI): calcd
by thin-layer chromatography and visualized by UV and a solu- for [C14H11ClO2S + Na]+: 301.0066, found 301.0069.
tion of KMnO4. Cinnamic acids 1a, 1g, 1j, 1k, 1n, 1q and sol-
(E)-1-Bromo-2-(2-(phenylsulfonyl)vinyl)benzene (3d).8 Color-
vents were obtained from commercial sources and used less solid, mp 77–79 °C (CH2Cl2–hexanes); Rf = 0.36 (1 : 3
without further purification. Unless otherwise noted, α,β-un- EtOAc–hexanes); IR (neat): ν 3049, 2918, 2849, 1603, 1584,
1
saturated carboxylic acid were synthesized according to literature 1447, 1437, 1299, 1282, 1142, 1083 cm−1; H NMR (400 MHz,
procedures via Wittig reaction and Horner–Wadsworth– CDCl3): δ 8.04 (d, J = 15.4 Hz, 1H), 7.95 (d, J = 8.7 Hz, 2H),
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7.64–7.59 (m, 2H), 7.55 (t, J = 7.8 Hz, 2H), 7.48 (dd, J = 7.7, 141.9 (C), 140.9 (C), 133.2 (CH), 129.8 (2 × CH), 129.6 (C), 129.3
1.5 Hz, 1H), 7.31–7.21 (m, 2H), 6.83 (d, J = 15.4 Hz, 1H); (2 × CH), 128.6 (2 × CH), 127.6 (2 × CH), 126.0 (CH), 21.5
13C NMR (100 MHz, CDCl3):
δ
141.0 (CH), 140.2 (C), (CH3); HRMS m/z (ESI): calcd for [C15H14O2S + Na]+: 281.0612,
133.6 (CH), 133.5 (CH), 132.5 (C), 132.0 (CH), 130.2 (CH), 129.4 found 281.0615.
(2 × CH), 128.2 (CH), 127.84 (2 × CH), 127.82 (CH), 125.6 (C);
(E)-2-(2-(Phenylsulfonyl)vinyl)phenol (3j).3d Colorless solid,
HRMS m/z (ESI): calcd for [C14H11BrO2S + Na]+: 346.9540, mp 151–152 °C (CH2Cl2–hexanes); Rf = 0.40 (1 : 1 EtOAc–
found 346.9546.
hexanes); IR (neat): ν 3317, 3100, 2921, 2851, 1602, 1580, 1444,
1
(E)-1-Bromo-4-(2-(phenylsulfonyl)vinyl)benzene (3e).3d Color- 1286, 1274, 1135, 1080 cm−1; H NMR (400 MHz, acetone-d6):
less solid, mp 138–139 °C (CH2Cl2–hexanes); Rf = 0.48 (1 : 3 δ 9.42 (s, 1H), 7.96 (d, J = 8.5 Hz, 2H), 7.92 (d, J = 15.5 Hz, 1H),
EtOAc–hexanes); IR (neat): ν 3054, 1610, 1582, 1481, 1446, 7.72–7.60 (m, 4H), 7.34 (d, J = 15.5 Hz, 1H), 7.29 (t, J = 7.7 Hz,
1397, 1305, 1141, 1067 cm−1 1H NMR (400 MHz, CDCl3): 1H), 6.99 (d, J = 8.2 Hz, 1H), 6.90 (t, J = 7.6 Hz, 1H); 13C NMR
;
δ 7.93 (d, J = 8.7 Hz, 2H), 7.64–7.50 (m, 6H), 7.33 (d, J = 8.5 Hz, (100 MHz, acetone-d6): δ 156.7 (C), 141.7 (C), 137.5 (CH), 132.8
2H), 6.84 (d, J = 15.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): (CH), 132.1 (CH), 129.9 (CH), 129.1 (2 × CH), 127.6 (CH), 127.1
δ 141.0 (CH), 140.4 (C), 133.5 (CH), 132.4 (2 × CH), 131.3 (C), (2 × CH), 119.8 (CH), 119.3 (C), 116.0 (CH); HRMS m/z (ESI):
129.9 (2 × CH), 129.4 (2 × CH), 128.0 (CH), 127.7 (2 × CH), calcd for [C14H12O3S + Na]+: 283.0405, found 283.0409.
125.6 (C); HRMS m/z (ESI): calcd for [C14H11BrO2S + Na]+:
(E)-3-(2-(Phenylsulfonyl)vinyl)phenol (3k). Pale yellow solid,
mp 86–88 °C (CH2Cl2–hexanes); Rf = 0.38 (1 : 1 EtOAc–
346.9540, found 346.9543.
(E)-1-Nitro-4-(2-(phenylsulfonyl)vinyl)benzene (3f).3d Yellow hexanes); IR (neat): ν 3417, 3051, 2923, 2853, 1589, 1443, 1288,
solid, mp 152–153 °C (CH2Cl2–hexanes); Rf = 0.35 (1 : 3 EtOAc– 1147, 1084 cm−1
hexanes); IR (neat): ν 3055, 1592, 1509, 1446, 1337, 1307, 1148, 8.6 Hz, 2H), 7.60–7.51 (m, 4H), 7.21 (t, J = 7.9 Hz, 1H),
1085 cm−1 1H NMR (400 MHz, acetone-d6): δ 8.28 (d, J = 7.00–6.95 (m, 2H), 6.89 (dd, J = 8.1, 1.9 Hz, 1H), 6.81 (d, J =
;
1H NMR (400 MHz, CDCl3): δ 7.91 (d, J =
;
8.9 Hz, 2H), 8.02–7.98 (m, 4H), 7.81 (d, J = 15.5 Hz, 1H), 15.4 Hz, 1H), 6.01 (br s, 1H); 13C NMR (100 MHz, CDCl3):
7.77–7.73 (m, 1H), 7.69–7.65 (m, 2H), 7.60 (d, J = 15.5 Hz, 1H); δ 156.3 (C), 142.6 (CH), 140.3 (C), 133.6 (C), 133.5 (CH), 130.3
13C NMR (100 MHz, acetone-d6): δ 149.0 (C), 140.7 (C), (CH), 129.4 (2 × CH), 127.6 (2 × CH), 127.1 (CH), 121.2 (CH),
139.3 (CH), 139.1 (C), 133.8 (CH), 132.4 (CH), 129.8 (2 × CH), 118.6 (CH), 114.9 (CH); HRMS m/z (ESI): calcd for [C14H12O3S
129.6 (2 × CH), 127.7 (2 × CH), 124.0 (2 × CH); HRMS m/z (ESI): + Na]+: 283.0405, found 283.0407.
calcd for [C14H11NO4S + Na]+: 312.0306, found 312.0309.
(E)-4-(2-(Phenylsulfonyl)vinyl)phenol (3l).3d Viscous oil; Rf =
(E)-1-(2-(Phenylsulfonyl)vinyl)-3-(trifluoromethyl)benzene 0.34 (1 : 1 EtOAc–hexanes); IR (neat): ν 3361, 3058, 2924, 1598,
1
(3g).9 Colorless solid, mp 83–85 °C (CH2Cl2–hexanes); Rf = 1582, 1512, 1444, 1279, 1134, 1080 cm−1; H NMR (400 MHz,
0.44 (1 : 3 EtOAc–hexanes); IR (neat): ν 3071, 2924, 1621, 1446, CDCl3): δ 7.91 (d, J = 7.4 Hz, 2H), 7.61–7.50 (m, 4H), 7.31 (d, J =
1431, 1325, 1301, 1139, 1068 cm−1; 1H NMR (400 MHz, CDCl3): 8.6 Hz, 2H), 6.83 (d, J = 8.6 Hz, 2H), 6.64 (d, J = 15.3 Hz, 1H);
δ 7.94 (d, J = 7.4 Hz, 2H), 7.70 (s, 1H), 7.67–7.60 (m, 4H), 13C NMR (100 MHz, CDCl3): δ 159.0 (C), 142.7 (CH), 140.8 (C),
7.56–7.49 (m, 3H), 6.95 (d, J = 15.5 Hz, 1H); 13C NMR 133.4 (CH), 130.7 (2 × CH), 129.4 (2 × CH), 127.5 (2 × CH),
(100 MHz, CDCl3): δ 140.5 (CH), 140.1 (C), 133.6 (CH), 133.1 124.7 (C), 123.8 (CH), 116.2 (2 × CH); HRMS m/z (ESI): calcd
(C), 131.6 (CH), 131.5 (q, J = 32.6 Hz, C), 129.7 (CH), 129.4 for [C14H12O3S + Na]+: 283.0405, found 283.0400.
(3 × CH), 127.7 (2 × CH), 127.5 (q, J = 4.0 Hz, CH), 124.9 (q, J =
4.0 Hz, CH), 122.1 (C); HRMS m/z (ESI): calcd for [C15H11F3O2S + Colorless solid, mp 101–102 °C (CH2Cl2–hexanes); Rf = 0.39
Na]+: 335.0330, found 335.0331.
(1 : 3 EtOAc–hexanes); IR (neat): ν 3075, 3046, 3005, 2838,
(E)-N,N-Dimethyl-4-(2-(phenylsulfonyl)vinyl)aniline (3h).10 1598, 1584, 1446, 1300, 1270, 1144, 1083 cm−1 1H NMR
(E)-1-Methoxy-3-(2-(phenylsulfonyl)vinyl)benzene
(3m).3a
;
Yellow solid, mp 158–159 °C (CH2Cl2–hexanes); Rf = 0.29 (400 MHz, CDCl3): δ 7.93 (d, J = 8.6 Hz, 2H), 7.66–7.59 (m, 2H),
(1 : 3 EtOAc–hexanes); IR (neat): ν 3045, 2896, 1581, 1519, 7.53 (t, J = 7.8 Hz, 2H), 7.29 (t, J = 7.9 Hz, 1H), 7.06 (d, J = 7.6
1302, 1285, 1139, 1080 cm−1 1H NMR (400 MHz, CDCl3): Hz, 1H), 6.97–6.93 (m, 2H), 6.83 (d, J = 15.4 Hz, 1H), 3.79
;
δ 7.91 (d, J = 8.6 Hz, 2H), 7.60–7.48 (m, 4H), 7.34 (d, J = 8.9 Hz, (s, 3H); 13C NMR (100 MHz, CDCl3): δ 159.9 (C), 142.4 (CH),
2H), 6.62 (d, J = 8.9 Hz, 2H), 6.55 (d, J = 15.2 Hz, 1H), 3.00 140.6 (C), 133.6 (C), 133.4 (CH), 130.1 (CH), 129.3 (2 × CH),
(s, 6H); 13C NMR (100 MHz, CDCl3): δ 152.2 (C), 143.3 (CH), 127.6 (2 × CH), 127.5 (CH), 121.2 (CH), 117.1 (CH), 113.3 (CH),
141.9 (C), 132.8 (CH), 130.4 (2 × CH), 129.1 (2 × CH), 127.3 55.3 (CH3); HRMS m/z (ESI): calcd for [C15H14O3S + Na]+:
(2 × CH), 120.6 (CH), 119.8 (C), 111.7 (2 × CH), 40.0 (2 × CH3); 297.0561, found 297.0567.
HRMS m/z (ESI): calcd for [C16H17NO2S + H]+: 288.1058, found
(E)-1-Methoxy-4-(2-(phenylsulfonyl)vinyl)benzene (3n).3d Color-
less solid, mp 100–101 °C (CH2Cl2–hexanes); Rf = 0.33 (1 : 3
288.1055.
(E)-1-Methyl-4-(2-(phenylsulfonyl)vinyl)benzene (3i).3d Color- EtOAc–hexanes); IR (neat): ν 3061, 2939, 2846, 1601, 1509,
less solid, mp 118–120 °C (CH2Cl2–hexanes); Rf = 0.49 (1 : 3 1444, 1260, 1138, 1081 cm−1 1H NMR (400 MHz, CDCl3):
;
EtOAc–hexanes); IR (neat): ν 3053, 2918, 1604, 1510, 1446, δ 7.92 (d, J = 8.8 Hz, 2H), 7.63–7.57 (m, 2H), 7.52 (t, J = 7.8 Hz,
1
1306, 1143, 1082 cm−1; H NMR (400 MHz, CDCl3): δ 7.93 (d, 2H), 7.41 (d, J = 8.7 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 6.69 (d, J =
J = 8.7 Hz, 2H), 7.66–7.58 (m, 2H), 7.53 (t, J = 7.8 Hz, 2H), 7.36 15.3 Hz, 1H), 3.81 (s, 3H); 13C NMR (100 MHz, CDCl3):
(d, J = 8.0 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 6.78 (d, J = 15.4 Hz, δ 162.1 (C), 142.3 (CH), 141.1 (C), 133.1 (CH), 130.4 (2 × CH),
1H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 142.5 (CH), 129.2 (2 × CH), 127.5 (2 × CH), 124.9 (C), 124.4 (CH), 114.5
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(2 × CH), 55.4 (CH3); HRMS m/z (ESI): calcd for [C15H14O3S + 105.8 (2 × CH), 61.0 (CH3), 56.2 (2 × CH3); HRMS m/z (ESI):
Na]+: 297.0561, found 297.0566.
calcd for [C17H18O5S + H]+: 335.0953, found 335.0954.
(E)-1,2-Dimethoxy-3-(2-(phenylsulfonyl)vinyl)benzene (3o).
(E)-1-(Allyloxy)-4-(2-(phenylsulfonyl)vinyl)benzene (3t). Color-
Colorless solid, mp 99–100 °C (CH2Cl2–hexanes); Rf = 0.31 less solid, mp 116–117 °C (CH2Cl2–hexanes); Rf = 0.48 (1 : 3
(1 : 3 EtOAc–hexanes); IR (neat): ν 3048, 2922, 2848, 1577, EtOAc–hexanes); IR (neat): ν 3054, 2919, 2856, 1599, 1569,
1
1463, 1445, 1426, 1282, 1271, 1141, 1058 cm−1
;
1H NMR 1505, 1304, 1238, 1173, 1141, 1082 cm−1; H NMR (400 MHz,
(400 MHz, CDCl3): δ 7.94–7.90 (m, 3H), 7.59 (t, J = 7.4 Hz, 1H), CDCl3): δ 7.92 (d, J = 8.7 Hz, 2H), 7.61 (d, J = 15.4 Hz, 1H),
7.52 (t, J = 7.8 Hz, 2H), 7.05–6.93 (m, 4H), 3.85 (s, 3H), 3.84 7.60–7.56 (m, 1H), 7.51 (t, J = 7.8 Hz, 2H), 7.40 (d, J = 8.8 Hz,
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 153.1 (C), 148.8 (C), 2H), 6.89 (d, J = 8.8 Hz, 2H), 6.69 (d, J = 15.4 Hz, 1H), 6.05–5.96
140.8 (C), 137.7 (CH), 133.2 (CH), 129.3 (2 × CH), 128.7 (CH), (m, 1H), 5.38 (dd, J = 17.3, 1.4 Hz, 1H), 5.28 (dd, J = 10.5,
127.6 (2 × CH), 126.4 (C), 124.2 (CH), 120.2 (CH), 114.9 (CH), 1.3 Hz, 1H), 4.54 (dt, J = 5.2, 1.4 Hz, 2H); 13C NMR (100 MHz,
61.2 (CH3), 55.9 (CH3); HRMS m/z (ESI): calcd for [C16H16O4S + CDCl3): δ 161.0 (C), 142.2 (CH), 141.1 (C), 133.2 (CH),
Na]+: 327.0667 found 327.0668.
132.5 (CH), 130.3 (2 × CH), 129.2 (2 × CH), 127.5 (2 × CH),
(E)-1,4-Dimethoxy-2-(2-(phenylsulfonyl)vinyl)benzene (3p).11 125.0 (C), 124.5 (CH), 118.1 (CH2), 115.2 (2 × CH), 68.8 (CH2);
Pale yellow solid, mp 120–122 °C (CH2Cl2–hexanes); Rf = 0.30 HRMS m/z (ESI): calcd for [C17H16O3S + Na]+: 323.0718, found
(1 : 3 EtOAc–hexanes); IR (neat): ν 3081, 2957, 2928, 2835, 323.0715.
1577, 1500, 1442, 1273, 1138, 1082, 1022 cm−1
;
1H NMR
(E)-2-(2-(Phenylsulfonyl)vinyl)naphthalene (3u).3a Pale yellow
(400 MHz, CDCl3): δ 7.93 (d, J = 8.7 Hz, 2H), 7.85 (d, J = solid, mp 89–90 °C (CH2Cl2–hexanes); Rf = 0.45 (1 : 3 EtOAc–
15.4 Hz, 1H), 7.60–7.57 (m, 1H), 7.52 (t, J = 7.7 Hz, 2H), 7.03 hexanes); IR (neat): ν 3046, 2919, 1611, 1445, 1304, 1286, 1139,
1
(d, J = 15.4 Hz, 1H), 6.92–6.90 (m, 2H), 6.84–6.82 (m, 1H), 3.81 1083 cm−1; H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 8.4 Hz,
(s, 3H), 3.74 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 153.4 (C), 2H), 7.92 (s, 1H), 7.85–7.79 (m, 4H), 7.63–7.49 (m, 6H), 6.96
153.3 (C), 141.1 (C), 138.3 (CH), 133.1 (CH), 129.2 (2 × CH), (d, J = 15.3 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 142.5 (CH),
128.1 (CH), 127.6 (2 × CH), 121.6 (C), 118.2 (CH), 114.9 (CH), 140.8 (C), 134.5 (C), 133.3 (CH), 133.1 (C), 130.9 (CH),
112.4 (CH), 55.9 (CH3), 55.8 (CH3); HRMS m/z (ESI): calcd for 129.8 (C), 129.3 (2 × CH), 128.9 (CH), 128.7 (CH), 127.8
[C16H16O4S + Na]+: 327.0667 found 327.0663.
(E)-5-(2-(Phenylsulfonyl)vinyl)benzo[d][1,3]dioxole
(2 × CH), 127.6 (2 × CH), 127.3 (CH), 127.0 (CH), 123.4 (CH);
(3q).12 HRMS m/z (ESI): calcd for [C18H14O2S + Na]+: 317.0612, found
Colorless solid, mp 95–96 °C (CH2Cl2–hexanes); Rf = 0.38 (1 : 3 317.0610.
EtOAc–hexanes); IR (neat): ν 3053, 2904, 1595, 1500, 1488,
(((1E,3E)-4-Phenylbuta-1,3-dien-1-yl)sulfonyl)benzene (3v).13
1447, 1307, 1257, 1139, 1082 cm−1; 1H NMR (400 MHz, CDCl3): Colorless solid, mp 89–90 °C (CH2Cl2–hexanes); Rf = 0.54 (1 : 3
δ 7.91 (d, J = 8.6 Hz, 2H), 7.61–7.50 (m, 4H), 6.98 (dd, J = 8.0, EtOAc–hexanes); IR (neat): ν 3057, 2921, 1615, 1584, 1446,
1.5 Hz, 1H), 6.91 (d, J = 1.5 Hz, 1H), 6.79 (d, J = 8.0 Hz, 1H), 1307, 1275, 1137, 1083 cm−1 1H NMR (400 MHz, CDCl3):
;
6.65 (d, J = 15.3 Hz, 1H), 5.98 (s, 2H); 13C NMR (100 MHz, δ 7.90 (d, J = 8.8 Hz, 2H), 7.59 (t, J = 8.4 Hz, 1H), 7.52 (t, J =
CDCl3): δ 150.4 (C), 148.5 (C), 142.2 (CH), 141.0 (C), 133.2 7.8 Hz, 2H), 7.45–7.39 (m, 3H), 7.37–7.31 (m, 3H), 6.97 (d, J =
(CH), 129.3 (2 × CH), 127.5 (2 × CH), 126.6 (C), 125.3 (CH), 15.5 Hz, 1H), 6.76 (dd, J = 15.5, 11.0 Hz, 1H), 6.43 (d, J =
124.9 (CH), 108.6 (CH), 106.8 (CH), 101.8 (CH2); HRMS m/z 14.7 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 143.0 (CH), 142.4
(ESI): calcd for [C15H12O4S + Na]+: 311.0354, found 311.0352.
(CH), 140.9 (C), 135.3 (C), 133.2 (CH), 129.7 (CH), 129.3
(E)-1,2,4-Trimethoxy-5-(2-(phenylsulfonyl)vinyl)benzene (3r). (3 × CH), 128.9 (2 × CH), 127.5 (2 × CH), 127.4 (2 × CH), 123.6
Pale yellow solid, mp 158–160 °C (CH2Cl2–hexanes); Rf = 0.28 (CH); HRMS m/z (ESI): calcd for [C16H14O2S + Na]+: 293.0612,
(1 : 1 EtOAc–hexanes); IR (neat): ν 3052, 2925, 2835, 1595, found 293.0611.
1514, 1446, 1296, 1211, 1138, 1083, 1029 cm−1
;
1H NMR
(E)-((2-Phenylprop-1-en-1-yl)sulfonyl)benzene (3w).14 Color-
(400 MHz, CDCl3): δ 7.92 (d, J = 7.4 Hz, 2H), 7.84 (d, J = less oil; Rf = 0.60 (1 : 3 EtOAc–hexanes); IR (neat): ν 3058, 2924,
15.4 Hz, 1H), 7.56–7.48 (m, 3H), 6.88–6.84 (m, 2H), 6.45 2853, 1601, 1572, 1444, 1300, 1140, 1083 cm−1 1H NMR
;
(s, 1H), 3.89 (s, 3H), 3.84 (s, 3H), 3.80 (s, 3H); 13C NMR (400 MHz, CDCl3): δ 7.96 (d, J = 8.6 Hz, 2H), 7.63–7.59 (m, 1H),
(100 MHz, CDCl3): δ 154.6 (C), 152.8 (C), 143.1 (C), 141.5 (C), 7.56–7.52 (m, 2H), 7.39–7.32 (m, 5H), 6.59 (d, J = 1.2 Hz, 1H),
138.1 (CH), 132.9 (CH), 129.1 (2 × CH), 127.4 (2 × CH), 2.51 (d, J = 1.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
124.6 (CH), 112.5 (C), 112.4 (CH), 96.4 (CH), 56.4 (CH3), δ 153.5 (C), 142.1 (C), 140.1 (C), 133.2 (CH), 129.9 (CH), 129.2
56.1 (CH3), 56.0 (CH3); HRMS m/z (ESI): calcd for [C17H18O5S + (2 × CH), 128.7 (2 × CH), 127.4 (CH), 127.2 (2 × CH), 126.3
Na]+: 357.0773, found 357.0770.
(E)-1,2,3-Trimethoxy-5-(2-(phenylsulfonyl)vinyl)benzene (3s). Na]+: 281.0612, found 281.0619.
Colorless solid, mp 143–144 °C (CH2Cl2–hexanes); Rf = 0.23
((2-Phenylallyl)sulfonyl)benzene (4w).15 Colorless oil; Rf
(1 : 3 EtOAc–hexanes); IR (neat): ν 3048, 2942, 2841, 1579, 0.53 (1 : 3 EtOAc–hexanes); IR (neat): ν 3060, 2926, 2853, 1446,
(2 × CH), 17.2 (CH3); HRMS m/z (ESI): calcd for [C15H14O2S +
=
1
1506, 1421, 1280, 1254, 1127, 1081 cm−1; H NMR (400 MHz, 1304, 1136, 1083 cm−1 1H NMR (400 MHz, CDCl3): δ 7.79
;
CDCl3): δ 7.93 (d, J = 8.5 Hz, 2H), 7.62–7.51 (m, 4H), 6.76 (d, J = (d, J = 8.5 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.44 (d, J = 8.0 Hz,
15.3 Hz, 1H), 6.69 (s, 2H), 3.840 (s, 3H), 3.837 (s, 6H); 13C NMR 2H), 7.28–7.23 (m, 5H), 5.60 (s, 1H), 5.23 (s, 1H), 4.28
(100 MHz, CDCl3): δ 153.5 (2 × C), 142.6 (CH), 140.8 (C), 133.3 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 138.7 (C), 138.4 (C),
(CH), 129.3 (2 × CH), 127.7 (2 × C), 127.6 (2 × CH), 126.3 (CH), 136.4 (C), 133.6 (CH), 128.9 (2 × CH), 128.6 (2 × CH), 128.4
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(2 × CH), 128.0 (CH), 126.2 (2 × CH), 121.9 (CH2), 62.0 (CH2); 118.9 (CH), 116.2 (CH), 111.2 (CH); HRMS m/z (ESI): calcd for
HRMS m/z (ESI): calcd for [C15H14O2S + Na]+: 281.0612, found [C12H11NO2S + Na]+: 256.0408, found 256.0404.
281.0611.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3aa).3d Colorless solid,
(E)-3-(2-(Phenylsulfonyl)vinyl)pyridine (3x).3d Pale yellow mp 117–118 °C (CH2Cl2–hexanes); Rf = 0.49 (1 : 3 EtOAc–hexanes);
solid, mp 83–85 °C (CH2Cl2–hexanes); Rf = 0.16 (1 : 1 EtOAc– IR (neat): ν 3045, 2921, 2851, 1613, 1595, 1449, 1302,
hexanes); IR (neat): ν 3060, 2920, 1617, 1445, 1410, 1304, 1144, 1140, 1084 cm−1
;
1H NMR (400 MHz, CDCl3): δ 7.81 (d, J =
1082 cm−1; H NMR (400 MHz, CDCl3): δ 8.70 (d, J = 1.8 Hz, 8.3 Hz, 2H), 7.64 (d, J = 15.4 Hz, 1H), 7.47–7.44 (m, 2H),
1H), 8.60 (dd, J = 4.7, 1.1 Hz, 1H), 7.93 (d, J = 7.4 Hz, 2H), 7.77 7.39–7.31 (m, 5H), 6.83 (d, J = 15.4 Hz, 1H), 2.41 (s, 3H);
(d, J = 8.0 Hz, 1H), 7.66 (d, J = 15.5 Hz, 1H), 7.61 (d, J = 7.3 Hz, 13C NMR (100 MHz, CDCl3): δ 144.4 (C), 141.9 (CH), 137.7 (C),
1H), 7.56–7.53 (m, 2H), 7.31 (dd, J = 8.0, 4.8 Hz, 1H), 6.94 (d, 132.4 (C), 131.1 (CH), 129.9 (2 × CH), 129.0 (2 × CH), 128.5
J = 15.5 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 151.8 (CH), (2 × CH), 127.7 (2 × CH), 127.6 (CH), 21.6 (CH3); HRMS
149.9 (CH), 140.2 (C), 138.7 (CH), 134.8 (CH), 133.7 (CH), 129.7 m/z (ESI): calcd for [C15H14O2S + Na]+: 281.0612, found
(CH), 129.4 (2 × CH), 128.3 (C), 127.8 (2 × CH), 123.8 (CH); 281.0618.
1
HRMS m/z (ESI): calcd for [C13H11NO2S + H]+: 246.0589, found
246.0591.
(E)-1-Chloro-4-(styrylsulfonyl)benzene (3ab).3d Colorless solid,
mp 78–80 °C (CH2Cl2–hexanes); Rf = 0.55 (1 : 3 EtOAc–
(E)-2-(2-(Phenylsulfonyl)vinyl)pyridine (3y).3d Colorless solid, hexanes); IR (neat): ν 3061, 3039, 1610, 1575, 1473, 1449,
mp 85–86 °C (CH2Cl2–hexanes); Rf = 0.20 (1 : 3 EtOAc– 1394, 1309, 1278, 1142, 1083 cm−1; 1H NMR (400 MHz, CDCl3):
hexanes); IR (neat): ν 3056, 1579, 1443, 1428, 1309, 1299, 1142, δ 7.87 (d, J = 8.6 Hz, 2H), 7.67 (d, J = 15.4 Hz, 1H), 7.51–7.46
1082 cm−1; H NMR (400 MHz, CDCl3): δ 8.59 (d, J = 4.4 Hz, (m, 4H), 7.43–7.36 (m, 3H), 6.82 (d, J = 15.4 Hz, 1H); 13C NMR
1
1H), 7.95 (d, J = 7.4 Hz, 2H), 7.72 (td, J = 7.7 Hz, J = 1.6 Hz, (100 MHz, CDCl3): δ 143.0 (CH), 140.1 (C), 139.2 (C), 132.1 (C),
1H), 7.66–7.59 (m, 2H), 7.53 (t, J = 7.8 Hz, 2H), 7.45–7.38 (m, 131.4 (CH), 129.6 (2 × CH), 129.1 (4 × CH), 128.6 (2 × CH),
2H), 7.28 (dd, J = 7.3, 5.1 Hz, 1H); 13C NMR (100 MHz, CDCl3): 126.8 (CH); HRMS m/z (ESI): calcd for [C14H11ClO2S + Na]+:
δ 151.0 (C), 150.3 (CH), 140.5 (CH), 140.2 (C), 137.0 (CH), 133.5 301.0066, found 301.0067.
(CH), 131.8 (CH), 129.3 (2 × CH), 127.9 (2 × CH), 125.5 (CH),
(E)-1-Methoxy-4-(styrylsulfonyl)benzene
(3ac).3a Colorless
125.0 (CH); HRMS m/z (ESI): calcd for [C13H11NO2S + H]+: solid, mp 75–76 °C (CH2Cl2–hexanes); Rf = 0.33 (1 : 3 EtOAc–
246.0589, found 246.0582.
hexanes); IR (neat): ν 3038, 2918, 2847, 1591, 1574, 1496, 1296,
1
(E)-2-(2-(Phenylsulfonyl)vinyl)furan (3z).3d Brown viscous 1260, 1135, 1082 cm−1; H NMR (400 MHz, CDCl3): δ 7.85 (d,
oil; Rf = 0.40 (1 : 3 EtOAc–hexanes); IR (neat): ν 3058, 1781, J = 8.9 Hz, 2H), 7.61 (d, J = 15.4 Hz, 1H), 7.45–7.43 (m, 2H),
1
1722, 1621, 1446, 1304, 1138, 1082 cm−1; H NMR (400 MHz, 7.37–7.34 (m, 3H), 6.98 (d, J = 8.9 Hz, 2H), 6.83 (d, J = 15.4 Hz,
CDCl3): δ 7.90 (d, J = 7.5 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.51 1H), 3.84 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 163.5 (C),
(t, J = 7.5 Hz, 2H), 7.45 (d, J = 1.0 Hz, 1H), 7.42 (d, J = 15.0 Hz, 141.3 (CH), 132.4 (C), 132.1 (C), 131.0 (CH), 129.8 (2 × CH),
1H), 6.72 (d, J = 15.0 Hz, 1H), 6.68 (d, J = 3.4 Hz, 1H), 129.0 (2 × CH), 128.4 (2 × CH), 127.8 (CH), 114.5 (2 × CH),
6.46 (dd, J = 3.4, 1.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): 55.6 (CH3); HRMS m/z (ESI): calcd for [C15H14O3S + Na]+:
δ 148.7 (C), 145.6 (CH), 140.8 (C), 133.3 (CH), 129.3 (2 × CH), 297.0561, found 297.0568.
128.9 (CH), 127.5 (2 × CH), 124.7 (CH), 116.9 (CH), 112.6 (CH);
HRMS m/z (ESI): calcd for [C12H10O3S + H]+: 235.0429, found mp 67–68 °C (CH2Cl2–hexanes); Rf = 0.21 (1 : 3 EtOAc–
(E)-(2-(Methylsulfonyl)vinyl)benzene (3ad).3d Colorless solid,
235.0426.
hexanes); IR (neat): ν 3047, 3026, 2926, 1622, 1451, 1273, 1130,
1
(E)-2-(2-(Phenylsulfonyl)vinyl)thiophene (3za).3d Brown solid, 1113 cm−1; H NMR (400 MHz, CDCl3): δ 7.60 (d, J = 15.5 Hz,
mp 79–80 °C (CH2Cl2–hexanes); Rf = 0.44 (1 : 3 EtOAc– 1H), 7.50–7.48 (m, 2H), 7.42–7.39 (m, 3H), 6.91 (d, J = 15.5 Hz,
hexanes); IR (neat): ν 3119, 3038, 2919, 1599, 1443, 1418, 1306, 1H), 3.01 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 144.0 (CH),
1279, 1141, 1081 cm−1; H NMR (400 MHz, CDCl3): δ 7.91 (d, 132.1 (C), 131.4 (CH), 129.2 (2 × CH), 128.6 (2 × CH), 126.1
1
J = 8.7 Hz, 2H), 7.77 (d, J = 15.1 Hz, 1H), 7.61–7.57 (m, 1H), (CH), 43.3 (CH3); HRMS m/z (ESI): calcd for [C9H10O2S + Na]+:
7.52 (t, J = 7.8 Hz, 2H), 7.41 (d, J = 5.1 Hz, 1H), 7.29 (d, J = 205.0299, found 205.0300.
3.6 Hz, 1H), 7.04 (dd, J = 5.1, 3.7 Hz, 1H), 6.62 (d, J = 15.1 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 140.8 (C), 136.9 (C),
135.1 (CH), 133.3 (CH), 132.4 (CH), 130.0 (CH), 129.3 (2 × CH),
Acknowledgements
128.3 (CH), 127.5 (2 × CH), 125.3 (CH); HRMS m/z (ESI): calcd
for [C12H10O2S2 + Na]+: 273.0020, found 273.0016.
We thank the Thailand Research Fund (TRF-DBG5480017), the
(E)-2-(2-(Phenylsulfonyl)vinyl)-1H-pyrrole (3zb). Brown solid, Center of Excellence for Innovation in Chemistry (PERCH-CIC),
mp 98–99 °C (CH2Cl2–hexanes); Rf = 0.25 (1 : 3 EtOAc– the Office of the Higher Education Commission, Mahidol Uni-
hexanes); IR (neat): ν 3336, 3056, 2921, 1607, 1444, 1409, 1298, versity under the National Research Universities Initiative and
1
1137, 1084 cm−1; H NMR (400 MHz, CDCl3): δ 9.39 (br s, 1H), the Development and Promotion of Science and Technology
7.85 (d, J = 8.6 Hz, 2H), 7.59–7.54 (m, 2H), 7.49–7.45 (m, 2H), 6.92 Talent Project (DPST), the Institute for the Promotion of
(s, 1H), 6.59 (d, J = 3.9 Hz, 1H), 6.58 (d, J = 15.1 Hz, 1H), 6.25–6.23 Teaching Science and Technology for financial support. The
(m, 1H); 13C NMR (100 MHz, CDCl3): δ 141.5 (C), 133.03 (CH), authors also thank Ms. Vanalee Tansiri for her kind help in
133.01 (CH), 129.3 (2 × CH), 127.1 (2 × CH), 126.1 (C), 124.1 (CH), preparation of starting materials.
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