An improved synthesis of vinyl- and β-iodovinyl sulfones by a molecular iodine-mediated one-pot iodosulfonationdehydroiodination reaction

Article abstract of DOI:10.1080/00397911.2012.663448

An improved one-pot method to synthesize vinyl sulfones from unsaturated systems by using molecular iodine/sodium arenesulfinate/sodium acetate as reagents was described. Vinyl sulfones derived from styrene derivatives were generally obtained in good to excellent yields except for those bearing strong electron releasing substituent. Aliphatic alkenes and activated alkenes gave the corresponding vinyl sulfone products in moderate to good yields. Arylacetylenes yielded the respective β-iodovinyl sulfones in good yields while low yield was observed with aliphatic terminal alkyne. The potentials of the method entail simplicity, short reaction time, non-anhydrous reaction conditions, employing inexpensive, non-metallic reagent and integrating two reactions that are commonly accomplished separately into a single operation. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397911.2012.663448

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An Improved Synthesis of Vinyl- and β-
Iodovinyl Sulfones by a Molecular Iodine-
Mediated One-Pot Iodosulfonation-
Dehydroiodination Reaction
Tassaporn Sawangphon a , Praewpan Katrun a , Korbua
Chaisiwamongkhol a , Manat Pohmakotr a , Vichai Reutrakul a ,
Thaworn Jaipetch b , Darunee Soorukram a & Chutima Kuhakarn a
a Department of Chemistry and Center for Innovation in Chemistry
(PERCH-CIC), Faculty of Science, Mahidol University, Bangkok,
Thailand
b Mahidol University, Kanchanaburi Campus, Saiyok, Kanchanaburi,
Thailand
Accepted author version posted online: 08 Aug 2012.Version of
record first published: 06 Mar 2013.
To cite this article: Tassaporn Sawangphon , Praewpan Katrun , Korbua Chaisiwamongkhol , Manat
Pohmakotr , Vichai Reutrakul , Thaworn Jaipetch , Darunee Soorukram & Chutima Kuhakarn (2013):
An Improved Synthesis of Vinyl- and β-Iodovinyl Sulfones by a Molecular Iodine-Mediated One-Pot
Iodosulfonation-Dehydroiodination Reaction, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 43:12, 1692-1707
To link to this article: http://dx.doi.org/10.1080/00397911.2012.663448
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Synthetic Communications1, 43: 1692–1707, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2012.663448
AN IMPROVED SYNTHESIS OF VINYL- AND
b-IODOVINYL SULFONES BY A MOLECULAR
IODINE-MEDIATED ONE-POT IODOSULFONATION-
DEHYDROIODINATION REACTION
Tassaporn Sawangphon,1 Praewpan Katrun,1
Korbua Chaisiwamongkhol,1 Manat Pohmakotr,1
Vichai Reutrakul,1 Thaworn Jaipetch,2 Darunee Soorukram,1
and Chutima Kuhakarn1
1Department of Chemistry and Center for Innovation in Chemistry
(PERCH-CIC), Faculty of Science, Mahidol University, Bangkok, Thailand
2Mahidol University, Kanchanaburi Campus, Saiyok, Kanchanaburi,
Thailand
GRAPHICAL ABSTRACT
Abstract An improved one-pot method to synthesize vinyl sulfones from unsaturated systems by
using molecular iodine/sodium arenesulfinate/sodium acetate as reagents was described. Vinyl
sulfones derived from styrene derivatives were generally obtained in good to excellent yields
except for those bearing strong electron releasing substituent. Aliphatic alkenes and activated
alkenes gave the corresponding vinyl sulfone products in moderate to good yields. Arylacetyl-
enes yielded the respective b-iodovinyl sulfones in good yields while low yield was observed with
aliphatic terminal alkyne. The potentials of the method entail simplicity, short reaction time,
non-anhydrous reaction conditions, employing inexpensive, non-metallic reagent and integrat-
ing two reactions that are commonly accomplished separately into a single operation.
Supplemental materials are available for this article. Go to the publisher’s online edition
of Synthetic Communications1 to view the free supplemental file.
Keywords Alkenes; alkynes; iodine; sulfur; vinyl sulfones
Received December 27, 2011.
Address correspondence to Chutima Kuhakarn, Department of Chemistry and Center for
Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama VI Road,
Bangkok 10400, Thailand. E-mail: chutima.kon@mahidol.ac.th
1692

IODOSULFONATION-DEHYDROIODINATION REACTION
1693
INTRODUCTION
Sulfones have gained much attention in both organic synthesis and medicinal
chemistry because of their wide versatility as synthetic intermediates and interesting
biological activities.[1] In particular, vinyl sulfones are important moieties found in
various biologically active compounds[2] and useful synthetic synthons in organic
synthesis.[3] As a result, there are numerous efforts aiming at developing efficient
and mild methods for the synthesis of vinyl sulfones.[4] The most recent ones include
Ir(II)-catalyzed allylic substitution of allyl sulfinate and isomerization,[5a] copper-
catalyzed or NaIO4=KI=AcOH-mediated oxidation of sodium sulfinates,[5b,c] and
Pd(OAc)2-catalyzed conjugate addition.[5d] Recently, we reported synthesis of vinyl
sulfones and b-iodovinyl sulfones by the reaction of aryl sulfinate with alkenes
and alkynes using a combination of PhI(OAc)2=KI as reagents.[6] In the course of
our study, we found that vinyl sulfones can be obtained in one pot by using molecu-
lar iodine and sodium arenesulfinate as reagents in the presence of an external base.
Although a similar process has been previously reported,[4f–i] the reaction required
two steps and lengthy reaction time on some substrates and had modest substrate
´
scope. Even though Najera et al. later employed sodium toluenesulfinate tetra-
hydrate and iodine in methanol followed by treatment with alcoholic potassium
hydroxide for the conversion of styrene to (E)-b-tosylstyrene in one pot, detailed
study on substrate scope was not conducted.[4j] In recent years, many reactions have
been reported using iodine as promoter or catalyst.[7] In view of the importance of
vinyl sulfones and molecular iodine as economical reagent, we now report an
improved and convenient experimental procedure to synthesize vinyl sulfones and
b-iodovinyl sulfones from alkenes and alkynes by molecular iodine–mediated
one-pot iodosulfonation followed by base-induced dehydroiodination reaction.
RESULTS AND DISCUSSION
Initially, a reaction of 4-chlorostyrene and sodium p-toluenesulfinate was
investigated. Based on our previous study, acetonitrile was primarily chosen as a
solvent for the reaction.[6] When a mixture of 4-chlorostyrene (1a) and sodium
p-toluenesulfinate (3 equiv), iodine (1.5 equiv) and sodium acetate (1.5 equiv) was
stirred at room temperature for 1 h, the expected vinyl sulfone (2a) was obtained
in 71% isolated yield (Table 1, entry 1). When dichloromethane was employed
1
as the solvent, H-NMR of a crude product indicated that it was a mixture of b-
iodosulfone and vinyl sulfone (Table 1, entry 2). Elimination of HI to yield vinyl sul-
fone readily took place during purification by silica gel-column chromatography to
yield 2a in 85% yield. However, the product obtained slowly turned brown upon
standing at room temperature and its TLC characteristics showed additional spots.
This also happened when ethyl acetate was used as the solvent (Table 1, entry 3).
When the reaction was performed in refluxing acetonitrile, the production of 2a
was increased to 90% yield (Table 1, entry 4). At refluxing temperature, other
organic solvents including ethanol, tetrahydrofuran, ethyl acetate, toluene, and
chloroform gave inferior results (Table 1, entries 5–9). It should also mention that
moderate yield (50%) of 2a was obtained when water was used as the solvent
(Table 1, entry 10). Additionally, when sodium p-toluenesulfinate was employed in

1694
T. SAWANGPHON ET AL.
Table 1. Investigation of optimized reaction conditionsa
Entry
Base
Solvent
Temp. (ꢀC)
Yield (%)
1
2
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
DBU
CH3CN
CH2Cl2
EtOAc
CH3CN
EtOH
Rt
Rt
71
85
80
90
81
80
78
72
11
50
65
87
77
80
83
3
Rt
4
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
5
6
THF
7
EtOAc
Toluene
CHCl3
H2O
8
9
10
11
12
13
14
15
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
NEt3
NaHCO3
Na2CO3
K2CO3
aAll reactions were performed using 4-chlorostyrene (0.5 mmol), iodine (1.5 equiv), p-TolSO2Na (3.0
equiv), and base (1.5 equiv).
lesser amount, lower yields were obtained. The choice of base was also briefly
screened and the results are shown in Table 1 (entries 11–15).
Even though triethylamine (TEA) gave comparable results to those when
sodium acetate was employed as the base, the crude mixture was not clean, as shown
by its TLC characteristics. Based on the results shown in Table 1, the standard reac-
tion conditions are to use iodine (1.5 equiv), and sodium p-toluenesulfinate (3 equiv),
sodium acetate (1.5 equiv) in acetonitrile and bring the reaction mixture to reflux for
1 h. The synthetic utilities of the method were demonstrated by further exploration
of compatibility of different substrates (i.e., styrene derivatives, aliphatic alkenes,
activated alkenes, and alkynes). The results are summarized in Tables 2–5.
When structurally different styrene derivatives were exposed to the standard
reaction conditions, in most cases, the corresponding vinyl sulfone products were
obtained in good yields except for those substituted with electron-releasing substitu-
ents, in which case poor to moderate yields were obtained (Table 2). In case of
4-methoxystyrene, the competing reaction was the methoxy-assisted elimination of
iodine followed by addition of sodium p-toluenesulfinate to yield compound 2i0
(Scheme 1).
2- and 4-vinylpyridines (1m and n) also underwent the reaction to yield the cor-
responding vinyl sulfone products in good yields while a-methylstyrene (1o) led to
a mixture of allyl sulfone and E-vinyl sulfone (see Supporting Information, available
online, for nuclear Overhauser effect data of 2o) with the allyl sulfone being
a major product (Scheme 2). Efforts toward optimization to obtain vinyl sulfone
2o as a major product were not successful. It is worth mentioning that when either

IODOSULFONATION-DEHYDROIODINATION REACTION
1695
Table 2. Synthesis of vinyl sulfones derived from styrene derivativesa
Entry
Alkene 1
Ar1
Ar2
Product 2 (% yield)b
1
2
1a
1b
1c
1d
1e
1f
4-ClC6H4
3-ClC6H4
2-ClC6H4
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
p-Tol
Ph
2a(90)
2b(93)
3
2c (86)
2d (87)
2e (93)
2f (95)
2g (80)
2h (70)
2i (35)c
2j (91)
2k (97)
4
4-BrC6H4
3-FC6H4
5
6
3-O2NC6H4
C6H5
7
1g
1h
1i
8
4-CH3C6H4
4-CH3OC6H4
4-AcOC6H4
3-OHCC6H4
4-(ClCH2)C6H4
4-ClC6H4
9
10
11
12
13
14
15
16
17
18
19
1j
1k
1l
2 l (85)[Ar1 ¼ 4-(p-TolSO2CH2)C6H4]
1a
1b
1c
1d
1f
2aa (80)
2bb (92)
3-ClC6H4
2-ClC6H4
4-BrC6H4
Ph
Ph
2cc (84)
2dd (87)
Ph
Ph
3-O2NC6H4
C6H5
4-(ClCH2)C6H4
2ff (93)
2gg (78)
1g
1l
Ph
Ph
2ll (90)[Ar1 ¼ 4-(PhSO2CH2)C6H4]
aAll reactions were performed using styrene derivative (0.5 mmol).
bIsolated yields.
cProduct 2i0 was obtained in 33%.
compound 2o or 2o0 was treated with an excess amount of organic bases (i.e., Et3N
and DBU), an approximately 1:5 mixture of 2o:2o0 was obtained (1H NMR
monitoring).
In the case of aliphatic alkenes, 1-octene under standard reaction conditions
gave a mixture of the corresponding vinyl sulfone and b-iodosulfone as shown by
1HNMR (300 MHz), and only 37% yield of vinyl sulfone product was isolated after
purification. Thus, attempts to examine suitable reaction conditions were carried
out. After an extensive investigation, it was found that the reaction with 1-octene
required an excess amount of both iodine (3 equiv) and sodium arenesulfinate
(4 equiv) in refluxing acetonitrile for 1 h followed by addition of sodium acetate
(1.5 equiv), and vinyl sulfone derived from 1-octene was obtained in 70% isolated
yield. It is worth mentioning that lower yield (31%) was observed if sodium acetate
was added at the beginning of the reaction. Having established optimized reaction
conditions, we then subjected a collection of aliphatic alkenes to the reaction con-
ditions, and the results are summarized in Table 3. The corresponding vinyl sulfones
were obtained in moderate to good yields. It should also be emphasized that no iso-
merization to allylic sulfones were observed for vinyl sulfones 4b, 4c, and 4d. Even
though 1-phenylcyclohexene (3g) gave allylic sulfone 4g in moderate yield (61%),
cyclohexene (3h), in contrast, gave a mixture of b-iodosulfone adduct 4h0 (24%)

1696
T. SAWANGPHON ET AL.
Table 3. Synthesis of vinyl sulfones derived from aliphatic alkenesa
Entry
1
Alkene
Product
Yield (%)b
70 (38)d
3a
3b
4a
4b
2
3
55
55
3c
4c
4
5
6
3d
3e
3f
4d
4e
4f
58
50
67
7
3g
4g
61
8
3h
3h
4h0 4h
24 12
9c
4h
55
aAll reactions were performed by using alkene (0.5 mmol).
bIsolated yields.
c(1) p-TolSO2Na and I2 were premixed in acetonitrile (15 min) before cyclohexene (0.5 mmol) in aceto-
nitrile was added, reflux, 1 h then NaOAc (1.5 equiv), reflux, 30 min; (2) DBU (1.5 equiv, acetonitrile, rt,
30 min.
dThe reaction of 1-octene (3a) with iodine in methanol followed by treatment with methanolic potassium
hydroxide gave the corresponding vinyl sulfone in 38% yield.

IODOSULFONATION-DEHYDROIODINATION REACTION
1697
Table 4. Synthesis of vinyl sulfonesderived from activated alkenesa
Entry
1
Substrate
Product
Yield (%)b
59
5a
5b
5c
6a
6b
6c
2
3
70 (nd)c
65
4
5d
6d
71
5
6
5e
5f
6e
6f
53
39
6ga (E-isomer)
6gb (Z-isomer)
10
33
7
5g
aAll reactions were performed by using activated alkene (0.5 mmol).
bIsolated yields.
cThe reaction of n-butyl acrylate (5a) with iodine in methanol followed by treatment with methanolic
potassium hydroxide failed to provide the corresponding vinyl sulfone.
and vinyl sulfone 4h (12%) under similar reaction conditions (entries 7 and 8). Grat-
ifyingly, moderate yield (55%) of vinyl sulfone derived from cyclohexene was
obtained by premixing the sulfinate salt with iodine before cyclohexene was intro-
duced followed by a separated DBU-induced HI elimination step (entry 9).
Under similar reaction conditions to those used for aliphatic alkenes, activated
alkenes afforded the corresponding vinyl sulfones in variable yields, and the results
are summarized in Table 4. Moderate yields (53–71%) were obtained when a,b-
unsaturated alkyl esters and amide were employed as precursors (Table 4, entries
1–5). a,b-Unsaturated nitriles gave the corresponding vinyl sulfones in poor yield
(entry 6); methacrylonitrile gave a mixture of two geometrical isomers with the
Z-isomer being a major isomer (entry 7). The stereochemistry assigned for vinyl

1698
T. SAWANGPHON ET AL.
Table 5. Synthesis of b-iodovinylsulfones derived from alkynesa
Entry
Alkyne 7
R
Product 8 (% yield)b
1
2
3
4
5
7a
7b
7c
7d
7e
C6H5
8a (74)
8b (79)
8c (82)
8d (82)
8e (13)
4-O2NC6H4
4-CH3C6H4
4-CH3OC6H4
CH3(CH2)5
aAll reactions were performed using alkyne (0.5 mmol).
bIsolated yields.
sulfones 6d, 6ga, and 6gb was based on their NOE experiments (see Supporting
Information).
Because of the importance of b-halovinyl sulfones as synthetic intermediates in
organic synthesis,[8] our efforts also extended to the synthesis of b-iodovinyl sulfones
starting from the alkyne substrates. Under the reaction conditions used for styrene
derivatives, the corresponding b-iodovinyl sulfones derived from phenylacetylene
derivatives were obtained in acceptable yields (Table 5, entries 1–4) while poor yield
was observed with that derived from aliphatic alkyne (Table 5, entry 5). The stereo-
chemistry of 8e was assigned by its NOE experiments (see Supporting Information)
and was confirmed to be E isomer. The stereochemistry of compounds 8a–d was then
assigned on the basis of that of 8e.
Finally, similar to the previous works, the reaction was believed to mechanis-
tically proceed via radical pathway and the mechanism for the reaction is shown in
Scheme 3.[4f–k] Sodium arenesulfinate reacts with iodine to give arenesulfonyl iodide,
which undergoes homolytic cleavage under refluxing acetonitrile to yield an arenesul-
fonyl radical. Addition of the sulfonyl radical to olefin takes place chemoselectively
Scheme 1. Formation of compound 2i0.

IODOSULFONATION-DEHYDROIODINATION REACTION
1699
Scheme 2. Reaction of vinylpyridiens 1m and n and a-methylstyrene (1o).
to form a more stabilized carbon radical. Subsequent abstraction with iodine from
arenesulfonyl iodide affords b-iodosulfone, which yields vinyl sulfone after
base-promoted elimination of HI. In the case of cyclohexene, under standard reac-
tion conditions, the corresponding b-iodosulfone adducts most likely from the syn
isomer where both the hydrogen and the iodo groups are in antiperiplanar position
readily undergoes elimination of HI (via an E2 mechanism). For the anti isomer,
elimination of HI by the action of NaOAc via an E2 mechanism would lead to allyl
sulfone as a product. However, the allyl sulfone was not isolated from this reaction.
Therefore, for the reaction of cyclohexene without treatment with DBU, a mixture of
vinyl sulfone and b-iodovinyl sulfone was obtained. Vinyl sulfone can be obtained
after treatment of the crude mixture containing both b-iodosulfone and vinyl sulfone
with strong base (DBU). Because of the higher acidity of H neighboring to the sul-
fonyl group, DBU-mediated HI elimination yielded vinyl sulfone 4h as a product. It
is also believed that the iodosulfonation of 1-phenylcyclohexene proceeds in a similar
fashion but the corresponding b-iodosulfone adducts readily undergoes HI elimin-
ation under the reaction conditions to yield allyl sulfone as the product.
Scheme 3. Mechanistic pathway.

1700
T. SAWANGPHON ET AL.
CONCLUSION
We described an improved method for the synthesis of vinyl sulfones derived
from various types of unsaturated system by using molecular iodine and sodium are-
nesulfinate as reagents in the presence of an external base. The reaction integrates
two reactions into a single operation and was found to be suitable for a variety of
substrates. In view of the efficiency of the method, the present approach is direct,
convenient, and time efficient.
EXPERIMENTAL
All known compounds were characterized by 1H and 13C NMR, infrared (IR),
and mass spectroscopy, and their spectroscopic data were identical to those reported
in the literature: 2a, 2f, 2h, 2o, 2o0, 2aa, 2gg, 2oo, 2oo0, 6a;[9] 2b;[10] 2c, 2j, 8a, 8c–8e;[4l]
2d, 2cc, 4c, 4f, 6b–6d, 8b;[6] 2g, 4g, 4h;[4f] 2i;[11] 2m, 2n;[12] 2ff;[13] 2dd;[4v] 4a;[4k] 4b;[14]
4d;[15] 4e;[16] and 6f.[4y] All new compounds were characterized by 1H and 13C NMR,
1
IR, and high-resolution mass spectroscopy (HRMS). H and 13C NMR spectra
were run on Bruker DPX-300 and Bruker Avance 500 spectrometers in CDCl3
and acetone-d6. IR spectroscopy was carried out on a Perkin-Elmer GX FT-IR
system spectrometer, HRMS was carried out on a Bruker micro TOF spectrometer,
the elemental analysis was performed on a Perkin-Elmer elemental analyzer 2400
CHN, and melting points (uncorrected) were determined on an Electrothermal IA
9000 apparatus and Gallenkamp apparatus.
General Procedure A
I2 (190.4 mg, 0.75 mmol) was added to a suspension mixture of styrene deriva-
tive (or alkyne) (0.5 mmol), sodium arenesulfinate (1.5 mmol), and NaOAc (61.5 mg,
0.75 mmol) in CH3CN (2 mL), and the reaction mixture was vigorously stirred at
refluxing temperature for 1 h. Upon completion of the reaction, the reaction mixture
was quenched by the addition of saturated aqueous sodium thiosulfate (Na2S2O3)
(5 mL) and basified with saturated aqueous sodium hydrogen carbonate (NaHCO3)
(5 mL). Further stirring was followed by extraction with ethyl acetate (3 ꢁ 15 mL).
The combined organic extracts were washed with water (20 mL) and brine
(20 mL), dried (anhydrous MgSO4), filtered, and concentrated (aspirator). The resi-
due was purified by column chromatography (silica gel) to furnish the analytically
pure product, and all solids were recrystallized from hexanes=CH2Cl2.
(E)-1-Chloro-4-(2-tosylvinyl)benzene (2a). White solid. Mp: 148–149 ꢀC
(lit.[9] 151–152 ꢀC); Rf ¼ 0.23 (hexanes–EtOAc, 8.5:1.5). IR (KBr): 3055 (aromatic),
1613 (C C), 1592, 1489 and 1450 (aromatic), 1304 and 1143 (SO2). 1H NMR
=
(300 MHz, CDC13): d ¼ 7.75 (d, J ¼ 8.0 Hz, 2H), 7.53 (d, J ¼ 15.4 Hz, 1H),
7.35–7.26 (m, 6H), 6.76 (d, J ¼ 15.4 Hz, 1H), 2.36 (s, 3H). 13C NMR (75 MHz,
CDCl3): d ¼ 144.5, 140.4, 137.6, 137.1, 131.0, 130.0, 129.6, 129.3, 128.3, 127.7,
21.6. HRMS (ESI-TOF): m=z [M þ Naþ] calcd. for C15H13ClO2SNa: 315.0222;
found: 315.0214.

IODOSULFONATION-DEHYDROIODINATION REACTION
1701
(E)-1-Chloro-4-[2-(phenylsulfonyl)vinyl]benzene (2aa). White solid. Mp:
128–131 ꢀC (lit.[9] 133–134 ꢀC); Rf ¼ 0.15 (hexanes–EtOAc, 9:1). IR (KBr): 3050 (aro-
1
matic), 1616 (C C), 1586, 1486 and 1447 (aromatic), 1309 and 1149 (SO2). H NMR
=
(300 MHz, CDC13): d ¼ 7.96 (d, J ¼ 7.3 Hz, 2H), 7.67–7.53 (m, 4H), 7.43–7.33 (m,
4H), 6.89 (d, J ¼ 15.5 Hz, 1H). 13C NMR (75 MHz, CDCl3): d ¼ 140.9, 140.5,
137.2, 133.5, 130.9, 129.7, 129.4, 128.0, 127.7. HRMS (ESI-TOF): m=z [M þ Naþ]
calcd. for C14H11ClO2SNa: 301.0066; found: 301.0042.
(E)-1-Chloro-3-[2-(phenylsulfonyl)vinyl]benzene (2bb). White solid. Mp:
98–100 ꢀC; Rf ¼ 0.30 (hexanes–EtOAc, 8.5:1.5). IR (KBr): 3048 (aromatic), 1618
(C C), 1565, 1479 and 1448 (aromatic), 1300 and 1145 (SO2). 1H NMR
=
(500 MHz, CDC13): d ¼ 7.97 (d, J ¼ 8.2 Hz, 2H), 7.68–7.62 (m, 2H), 7.60–7.57 (m,
2H), 7.48 (s, 1H), 7.41–7.33 (m, 3H), 6.91 (d, J ¼ 15.4 Hz, 1H). 13C NMR
(125 MHz, CDCl3): d ¼ 140.7, 140.4, 135.1, 134.2, 133.5, 131.0, 130.3, 129.4, 129.0,
128.1, 127.7, 126.8. HRMS (ESI-TOF): m=z [M þ Naþ] calcd. for C14H11ClO2SNa:
301.0075; found: 301.0042.
(E)-1-Fluoro-3-(2-tosylvinyl)benzene (2e). White solid. Mp: 75–78 ꢀC;
=
Rf ¼ 0.50 (hexanes–EtOAc, 4:1). IR (KBr,): 3053 (aromatic), 1617 (C C), 1600
1
and 1509 (aromatic), 1304 and 1142 (SO2). H NMR (300 MHz, CDC13): d ¼ 7.84
(d, J ¼ 8.4 Hz, 2H) 7.62 (d, J ¼ 15.4 Hz, 1H), 7.41–7.31 (m, 3H), 7.27 (d, J ¼ 8.3 Hz,
Hz, 1H), 7.20-7.08 (m, 2H), 6.88 (d, J ¼ 15.4 Hz, 1H), 2.45 (s, 3H). 13C NMR
(75 MHz, CDCl3): d ¼ 162.9, 144.6, 140.3, 137.3, 134.6, 130.6, 130.0, 129.1, 127.7,
124.5, 117.9, 114.7, 21.6. HRMS (ESI-TOF): m=z [M þ Naþ] calcd for
C15H13FO2SNa: 299.0518; found: 299.0473.
o
(E)-1-Methoxy-4-(2-tosylvinyl)benzene (2i). White solid. Mp: 177–180 C
(lit.[11] 178–180 ꢀC); Rf ¼ 0.28 (hexanes–EtOAc, 4:1). IR (KBr): 3053 (aromatic),
=
1601 (C C), 1510 and 1464 (aromatic), 1303 and 1141 (SO2), 1258 and 1087
(C-O). 1H NMR (300 MHz, CDCl3): d ¼ 7.82 (d, J ¼ 8.0 Hz, 2H), 7.60 (d, J ¼ 15.4 Hz,
Hz, 1H), 7.42 (d, J ¼ 8.6, 2H), 7.33 (d, J ¼ 8.0 Hz, 2H), 6.89 (d, J ¼ 8.7 Hz, 2H), 6.71
(d, J ¼ 15.4 Hz, 1H), 3.85 (s, 3H), 2.44 (s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 162.0,
144.1, 141.7, 138.2, 130.3, 129.9, 127.5, 125.1, 124.9, 114.5, 55.4, 21.5. HRMS
(ESI-TOF): m=z [M þ Naþ] calcd for C16H16O3SNa: 311.0718; found: 311.0706.
4,4’-(1-(4-Methoxyphenyl)-ethane-1,2-diyldisulfonyl)bis-(methylben-
zene) (2i’). White solid. Mp: 124–125 oC; Rf ¼ 0.14 (hexanes–EtOAc, 4:1). IR
(KBr): 2976 and 2923 (C-H of aromatic), 1597, 1516, and 1453 (aromatic), 1305
1
and 1136 (SO2), 1251 and 1082 (C-O). H NMR (300 MHz, CDCl3): d ¼ 7.44 (d,
J ¼ 8.3 Hz, 2H), 7.39 (d, J ¼ 8.3 Hz, 2H), 7.21 (d, J ¼ 8.5, 2H), 7.14 (d, J ¼ 8.5 Hz,
2H), 6.86 (d, J ¼ 8.8 Hz, 2H), 6.61 (d, J ¼ 8.8 Hz, 2H), 4.55 (dd, J ¼ 12.0, 2.5 Hz,
1H), 4.11 (dd, J ¼ 14.3, 2.5 Hz, 1H), 3.91 (dd, J ¼ 14.3, 12.0 Hz, 1H), 3.77 (s, 3H),
2.42 (s, 3H), 2.39 (s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 160.2, 145.1, 144.5,
136.2, 133.1, 131.0, 129.5, 129.1, 127.8, 121.0, 113.7, 65.6, 55.1, 54.0, 21.5, 21.4.
HRMS (ESI-TOF): m=z [M þ Naþ] calcd for C23H24O5S2Na: 467.0963; found:
467.1028.
(E)-3-(2-Tosylvinyl)benzaldehyde (2k). White solid. Mp: 137–140 ꢀC;
Rf ¼ 0.18 (hexanes–EtOAc, 7:3). IR (KBr): 3049 (aromatic), 2927 (aliphatic), 1688

1702
T. SAWANGPHON ET AL.
1
=
=
(C O), 1619 (C C), 1596, 1482 and 1450 (aromatic), 1303 and 1144 (SO2). H NMR
(300 MHz, CDC13): d ¼ 10.04 (s, 1H), 7.99 (s, 1H), 7.92 (d, J ¼ 7.4 Hz, 1H), 7.86 (d,
J ¼ 8.2 Hz, 2H), 7.74 (d, J ¼ 7.4 Hz, 1H), 7.72 (d, J ¼ 15.4 Hz, 1H), 7.60 (t, J ¼ 7.7 Hz,
1H), 7.38 (d, J ¼ 8.2 Hz, 2H), 6.99 (d, J ¼ 15.4 Hz, 1H), 2.46 (s, 3H). 13C NMR
(75 MHz, CDCl3): d ¼ 191.3, 144.7, 140.0, 137.2, 136.9, 134.0, 133.5, 131.9, 130.1,
129.9, 129.7, 128.9, 127.8, 21.6. HRMS (ESI-TOF): m=z [M þ Naþ] calcd. for
C16H14O3SNa: 309.0561; found: 309.0524.
(E)-1-Methyl-4-f[4-(tosylmethyl)styryl]sulfonylgbenzene (2l). White
solid. Mp: 77–79 ꢀC; Rf ¼ 0.20 (hexanes–EtOAc, 7:3). IR (KBr): 3043 (aromatic),
=
2925 (aliphatic), 1610 (C C), 1597, 1494 and 1446 (aromatic), 1303 and 1147
(SO2) cmꢂ1. H NMR (300 MHz, CDC13): d ¼ 7.79 (d, J ¼ 8.2 Hz, 2H), 7.57 (d,
1
J ¼ 15.5 Hz, 1H), 7.48 (d, J ¼ 8.2 Hz, 2H), 7.35–7.31 (m, 4H), 7.21 (d, J ¼ 8.1 Hz,
2H), 7.10 (d, J ¼ 8.1 Hz, 2H), 6.85 (d, J ¼ 15.5 Hz, 1H), 4.28 (s, 2H), 2.40 (s, 3H),
2.38 (s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 145.0, 144.6, 140.8, 137.5, 134.8,
132.8, 131.5, 131.3, 130.0, 129.7, 128.56, 128.55, 127.8, 62.6, 21.64, 21.62. HRMS
(ESI-TOF): m=z [M þ Naþ] calcd. for C23H22O4S2Na: 427.1038; found: 427.1040.
(E)-1-[(Phenylsulfonyl)methyl]-4-[2-(phenylsulfonyl)vinyl]benzene (2ll).
White solid. Mp: 160–162 ꢀC; Rf ¼ 0.13 (hexanes–EtOAc, 7:3). IR (KBr): 3050 (aro-
1
matic), 1615 (C C), 1583, 1481 and 1447 (aromatic), 1299 and 1148 (SO2). H NMR
=
(300 MHz, CDC13): d ¼ 7.97 (d, J ¼ 7.3 Hz, 2H), 7.67–7.56 (m, 7H), 7.48 (t,
J ¼ 7.3 Hz, 2H), 7.40 (d, J ¼ 8.1 Hz, 2H), 7.14 (d, J ¼ 8.1 Hz, 2H), 6.88 (d,
J ¼ 15.4 Hz, 1H), 4.34 (s, 2H). 13C NMR (75 MHz, CDCl3): d ¼ 141.3, 140.4,
137.7, 134.0, 133.5, 132.8, 131.5, 131.2, 129.4, 129.1, 128.6, 128.5, 128.3, 127.7,
62.5. HRMS (ESI-TOF): m=z [M þ Naþ] calcd. for C21H18O4S2Na: 421.0544; found:
421.0602.
General Procedure B
I2 (380.7 mg, 1.5 mmol) was added to a suspension mixture of aliphatic alkene
(or activated alkene) (0.5 mmol) and p-TolSO2Na (356.4 mg, 2.0 mmol) in CH3CN
(2 mL), and the reaction mixture was vigorously stirred at refluxing temperature
for 1 h. After cooling to room temperature, NaOAc (61.5 mg, 0.75 mmol) was added
and the reaction mixture was vigorously stirred at refluxing temperature for 0.5 h.
Upon completion of the reaction, the reaction mixture was quenched by the addition
of saturated aqueous sodium thiosulfate (Na2S2O3) (5 mL), and basified with satu-
rated aqueous sodium hydrogen carbonate (NaHCO3) (5 mL). Further stirring was
followed by extraction with ethyl acetate (3 ꢁ 15 mL). The combined organic extracts
were washed with water (20 mL) and brine (20 mL), dried (anhydrous MgSO4), fil-
tered, and concentrated (aspirator). The residue was purified by column chromato-
graphy (silica gel) to furnish the analytically pure product and all solids were
recrystallized from hexanes=CH2Cl2.
(E)-1-Methyl-4-(oct-1-en-1-ylsulfonyl)benzene (4a). Colorless oil (lit.[4k]
colorless viscous liquid); Rf ¼ 0.50 (hexanes–EtOAc, 9:1). IR (neat): 3047 (aromatic),
=
2929 and 2858 (aliphatic), 1634 (C C), 1597, 1495 and 1457 (aromatic), 1303 and
1146 (SO2).1H NMR (300 MHz, CDC13): d ¼ 7.75 (d, J ¼ 8.3 Hz, 2H), 7.32 (d,

IODOSULFONATION-DEHYDROIODINATION REACTION
1703
J ¼ 8.0 Hz, 2H), 6.95 (dt, J ¼ 15.1, 6.9 Hz, 1H), 6.29 (d, J ¼ 15.1 Hz, 1H), 2.42 (s,
3H), 2.21 (q, J ¼ 6.7 Hz, 2H), 1.46–1.39 (m, 2H), 1.30–1.25 (m, 6H), 0.85 (br t,
J ¼ 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 146.6, 144.0, 137.7, 130.5,
129.72, 129.67, 127.4, 31.3, 28.5, 27.4, 22.3, 21.4, 13.8. HRMS (ESI-TOF): m=z
[M þ Naþ] calcd. for C15H22O2SNa: 289.1238; found: 289.1188.
(E)-3-Tosylacrylamide (6e). White solid. Mp: 184–187 ꢀC; Rf ¼ 0.18
=
(hexanes–EtOAc, 4:1). IR (KBr): 3416 (N-H) 3070 (aromatic), 1678 (C O), 1619
=
(C C), 1601, 1490 and 1440 (aromatic), 1307 and 1150 (SO2). 1H NMR
(300 MHz, acetone-d6): d ¼ 7.81 (d, J ¼ 8.3 Hz, 2H), 7.60–7.40 (br, 1H), 7.48 (d,
J ¼ 8.0 Hz, 2H), 7.32 (d, J ¼ 14.9 Hz, 1H), 7.01 (d, J ¼ 14.9 Hz, 1H), 7.05–6.85 (br,
1H), 2.44 (s, 3H). 13C NMR (75 MHz, acetone-d6): d ¼ 164.1, 146.1, 141.1, 137.6,
134.9, 131.0, 128.9, 21.5. HRMS (ESI-TOF): m=z [M þ Naþ] calcd. for
C10H11NO3SNa: 248.0357; found: 248.0327.
(E)-2-Methyl-3-tosylacrylonitrile (6ga). White solid. Mp: 93–94 ꢀC;
Rf ¼ 0.25 (hexanes–EtOAc, 8.5:1.5). IR (KBr): 3038 (aromatic), 2924 (aliphatic),
2233 (CꢃN), 1594 and 1440 (aromatic), 1299 and 1149 (SO2). 1H NMR
(300 MHz, CDCl3): d ¼ 7.82 (d, J ¼ 8.4 Hz, 2H), 7.43 (d, J ¼ 8.0 Hz, 2H), 6.89 (d,
J ¼ 1.6 Hz, 1H), 2.50 (s, 3H), 2.42 (s, 3H). 13C NMR (75 MHz, CDCl3): d ¼ 146.0,
143.1, 136.8, 130.4, 127.9, 123.2, 117.1, 21.6, 16.4. HRMS (ESI-TOF): m=z
[M þ Naþ] calcd. for C11H11NO2SNa: 244.0408; found: 244.0381.
(Z)-2-methyl-3-tosylacrylonitrile (6gb). White solid. Mp: 112–114 ꢀC;
Rf ¼ 0.10 (hexanes–EtOAc, 8.5:1.5). IR (KBr): 3038 (aromatic), 2924 (aliphatic),
1
=
2233 (CꢃN), 1619 (C C), 1594 and 1441 (aromatic), 1307 and 1149 (SO2). H
NMR (300 MHz, CDCl3): d ¼ 7.88 (d, J ¼ 8.4 Hz, 2H), 7.41 (d, J ¼ 8.0 Hz, 2H),
6.87 (q, J ¼ 1.6 Hz, 1H), 2.47 (s, 3H), 2.16 (d, J ¼ 1.6 Hz, 3H). 13C NMR (75 MHz,
CDCl3): d ¼ 145.9, 142.9, 135.9, 130.2, 128.2, 121.1, 114.2, 22.3, 21.6. HRMS
(ESI-TOF): m=z [M þ Naþ] calcd. for C11H11NO2SNa: 244.0408; found: 244.0376.
ACKNOWLEDGMENTS
Financial support from the Thailand Research Fund (TRF; DBG5480817), Center
of Excellence for Innovation in Chemistry (PERCH-CIC), and Mahidol University
under the National Research Universities Initiative is gratefully acknowledged.
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