PhI(OAc)2/KI-mediated reaction of aryl sulfinates with alkenes, alkynes, and α,β-unsaturated carbonyl compounds: Synthesis of vinyl sulfones and β-iodovinyl sulfones

Article abstract of DOI:10.1002/ejoc.201000641

(Diacetoxyiodo)benzene [PhI(OAc)₂, DIB] was able to promote the reaction of sodium aryl sulfinate and potassiumiodide (KI) with alkenes and alkynes to afford the corresponding vinyl sulfones and β-iodovinyl sulfones, respectively, in good yield

Full text of DOI:10.1002/ejoc.201000641

FULL PAPER
DOI: 10.1002/ejoc.201000641
PhI(OAc)2/KI-Mediated Reaction of Aryl Sulfinates with Alkenes, Alkynes,
and α,β-Unsaturated Carbonyl Compounds: Synthesis of Vinyl Sulfones and
β-Iodovinyl Sulfones
Praewpan Katrun,[a] Supanimit Chiampanichayakul,[a] Kanokwan Korworapan,[a]
Manat Pohmakotr,[a] Vichai Reutrakul,[a] Thaworn Jaipetch,[b] and Chutima Kuhakarn*[a]
Keywords: Alkynes / Alkenes / Iodine / Sulfur
(Diacetoxyiodo)benzene [PhI(OAc)2, DIB] was able to pro-
mote the reaction of sodium aryl sulfinate and potassium
tively, in good yields. The salient features of this reaction are
that it employs a commercially available and environmen-
iodide (KI) with alkenes and alkynes to afford the corre- tally benign hypervalent iodine(III) reagent, a one-step reac-
sponding vinyl sulfones and β-iodovinyl sulfones, respec- tion, a short reaction time, and mild reaction conditions.
acetylenic sulfones,[14] selenosulfonation to alkynes,[15] nu-
cleophilic addition to 1-phenylseleno-2-(arenesulfonyl)-
Introduction
ethyne,[16] addition of sodium benzenesulfinate to alkynyl-
selenonium salts,[17] displacement of β-bromostyrene deriv-
atives with sodium arenesulfinate,[18] reaction of alkenyltri-
phenylbismuthonium tetrafluoroborates with aryl sulfin-
ate,[19] reaction of β-haloalkenylphenyliodonium salts with
sodium benzenesulfinate,[20] palladium-catalyzed reac-
tions,[21] copper-catalyzed reactions,[22] cross-metathesis re-
actions,[23] carbomagnesiation of acetylenic sulfones,[24] and
reaction of 1,2-dibromoalkanes with sulfinic acid sodium
salts.[25] Considering the importance of vinyl sulfones both
as reactive synthons and as biologically active moieties in
vinyl sulfone containing compounds, it is still of high inter-
est to develop simple and efficient methods for the synthesis
of vinyl sulfones.
During the past two decades, the versatility of hyperval-
ent iodine reagents in organic synthesis is well recognized
owing to their mild, highly selective, and environmentally
benign properties for effecting a number of oxidative trans-
formations.[26] Currently, both iodine(V) and iodine(III)
reagents are widely used in organic synthesis. Despite their
intriguing synthetic applications, widely used iodine(V) rea-
gents are potentially explosive. As a result, iodine(III) rea-
gents have received much more attention and have found
broad application in organic synthesis.[27] One of the most
important and commercially available iodine(III) reagents
is (diacetoxyiodo)benzene [PhI(OAc)2], which has several
commonly used abbreviations, such as BAIB, DIB, PIDA,
IBD, or IBDA. It is easy to handle, nontoxic, commercially
available, and comparable in reactivity to heavy metal con-
taining reagents. The synthetic utilities of PhI(OAc)2 as an
efficient oxidizing agent have been demonstrated by several
groups.[28] The combination of PhI(OAc)2 with halide salts
has been reported for electrophilic halogenations of sub-
Vinyl sulfones are important units in organic synthesis
due to the chemical versatility of the sulfonyl moiety.[1] The
sulfonyl group, similar to the carbonyl group, has an activa-
ting effect to the adjacent double bonds or triple bonds,
which enables these compounds to serve as Michael ac-
ceptors[2] and electron-deficient ene partners[3] in cycload-
dition reactions. Vinyl sulfone containing molecules have
been shown to exhibit important biological activities; for
example, cysteine protease inhibitors,[4] HIV-1 inhibitors,[5]
and inhibitors of a transpeptidase required for cell wall pro-
tein anchoring and virulence in Staphylococcus aureus.[6] In
addition, the sulfonyl group can be exchanged by hydrogen,
an alkyl group, a hydroxy group, a carbonyl group, or a
nucleophile, and it is also susceptible to β-elimination and
sulfur dioxide extrusion, allowing the sulfonyl group to
function as a temporary activating functional group.[7]
A
number of synthetic routes are available toward the synthe-
sis of vinyl sulfones including: a two-step method involving
β-elimination of and sulfur oxidation or vice versa,[8] ad-
dition of PhSO2X (X = I, Cl, SePh, ONO2, HgCl, etc.) to
alkenes followed by β-elimination,[9] addition of PhSO2X
(X = I, Cl, etc.) to alkynes,[10] Horner–Wadsworth–Em-
mons reaction of carbonyl compounds and sulfonyl phos-
phoranes,[11] hydrozirconation reaction of acetylenic sul-
fones,[12] hydrozirconation of terminal alkynes followed by
reaction with sulfonyl chloride,[13] hydrotelluration of
[a] Department of Chemistry and Center for Innovation in Chem-
istry (PERCH-CIC), Faculty of Science, Mahidol University,
Rama 6 Road, Bangkok 10400, Thailand
E-mail: scckk@mahidol.ac.th
[b] Mahidol University, Kanchanaburi Campus,
Saiyok, Kanchanaburi 71150, Thailand
Supporting information for this article is available on the
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C. Kuhakarn et al.
FULL PAPER
strates, particularly olefins, followed by nucleophilic-as- 2a was observed when the amount of PhI(OAc)2 employed
sisted halonium ion ring opening.[29]
was as low as 1.5 equiv., however, with a prolonged reaction
time (Table 1, Entry 14 vs. 10).
Having established the most efficient reaction conditions
(Table 1, Entry 14), we next investigated the efficiency of
some hypervalent iodine reagents and types of additives,
and the results are listed in Table 2. When using Et4NI as
Results and Discussion
As a part of our ongoing research on the chemistry of
hypervalent iodine reagents,[30] we herein describe our work
on the development of a vinyl sulfone protocol by PhI-
(OAc)2/KI-mediated reaction of aryl sulfinates with alkenes
and alkynes. Our experiment was first conducted by using
styrene and sodium p-toluenesulfinate as model substrates
to search for optimum reaction conditions (Table 1).
Table 2. Optimization of hypervalent iodine reagents and addi-
tives.[a]
The reaction was initially carried out in water by using
PhI(OAc)2 (2.2 equiv.) and Et4NI (1 equiv.) as an additive
and sodium p-toluenesulfinate (4 equiv.; Table 1, Entry 1).
A facile reaction took place within 30 min to yield β-iodo-
sulfone 3a and expected α,β-unsaturated sulfone 2a in a ra-
tio of 19:1. Higher conversion to α,β-unsaturated sulfone
2a was observed when the reaction time was extended from
0.5 to 3 h (Table 1, Entry 2). The reactions conducted in
aqueous CH3CN, aqueous THF, and CH3OH gave compar-
able results, and a mixture of 2a and 3a was obtained
(Table 1, Entries 3–5). Gratifying, when EtOAc was em-
ployed as the solvent, 2a was obtained as the major product
(2a/3a = 2:1). Among organic solvents screened, CH3CN
gave the best result (Table 1, Entries 7–10), yielding 2a in
90% yield after chromatographic purification (Table 1, En-
try 10). A slightly lower yield was observed when the reac-
tion was carried out with a shorter reaction time or with a
decrease in the loading of PhI(OAc)2 from 2.2 to 1.1 equiv.
(Table 1, Entries 11 and 12). Decreasing the stoichiometry
of sodium p-toluenesulfinate led to a dramatic decrease in
Entry
Hypervalent iodine
Additive
Ratio[b]
2a/3a
Yield of 2a[c]
[%]
1
2
3
4
5
6
7
PhI(OAc)2
IBX
Et4NI
Et4NI
Et4NI
Bu4NI
LiI
91[d]
62[d]
PhI(OCOCF3)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
1:3
88[d]
2:1
4:1
NaI
KI
85[d]
[a] All reactions were performed by using styrene (0.5 mmol), pTol-
SO2Na (4 equiv.), hypervalent iodine reagent (1.5 equiv.), and addi-
tive (1 equiv.) in CH3CN at room temperature for 1 h. [b] Product
ratios were calculated from integration of the signals in the 1H
NMR (300 MHz) spectrum of the crude product. [c] Isolated yields
after chromatographic purification. [d] The formation of 3a was
not observed by 1H NMR (300 MHz) spectroscopic analysis of the
the reaction yield (Table 1, Entry 13). An excellent yield of crude products.
Table 1. Optimization of reaction conditions.[a]
Entry
PhI(OAc)2
[equiv.]
pTolSO2Na
[equiv.]
Solvent
Time
[h]
Ratio[b]
2a/3a
Yield of 2a[c]
[%]
1
2
3
4
5
6
7
8
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
1.1
2.2
1.5
4
4
4
4
4
4
4
4
4
4
4
4
2
4
H2O
H2O
0.5
3
0.5
0.5
0.5
3
0.5
0.5
5
0.5
0.25
0.5
0.5
1
1:19
1:7
2:5
2:3
1:3
2:1
H2O/CH3CN (1:3)
H2O/THF (1:3)
CH3OH
EtOAc
DMSO
CHCl3
CH2Cl2
CH3CN
CH3CN
CH3CN
CH3CN
64[d]
60[d]
58[d]
90[d]
80[d]
79[d]
33[d]
91[d]
9
10
11
12
13
14
CH3CN
[a] All reactions were performed by using styrene (0.5 mmol) and Et4NI (1 equiv.) at room temperature. [b] Product ratios were calculated
from integration of the signals in the 1H NMR (300 MHz) spectrum of the crude product. [c] Isolated yield after chromatographic
1
purification. [d] The formation of 3a was not observed by H NMR (300 MHz) spectroscopic analysis of the crude products.
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Vinyl Sulfones by PhI(OAc)2/KI-Mediated Reactions of Aryl Sulfinates
an additive, the iodine(V) reagent IBX gave inferior results of aliphatic alkenes including those containing an oxygen
(Table 2, Entry 2) and the reaction conversion was lowered atom (Table 4, Entries 1–3), a bromine atom (Table 4, En-
dramatically by utilizing PhI(OCOCF3)2 (Table 2, Entry 3). tries 4 and 5), an aldehyde function (Table 4, Entry 6), and
Among the hypervalent iodine reagents tested, and on the a 1,3-dioxane moiety (Table 4, Entry 7) gave the corre-
basis of both efficiency and availability of hypervalent io- sponding products in good yields (70–89%). Allyl phenyl
dine compounds, PhI(OAc)2 was chosen as the oxidant for ether and allylbenzene derivatives yielded products derived
this reaction. The effect of additives was also briefly investi- from double bond isomerization as major products
gated. Even though tetraalkylammonium iodide salts gave (Table 4, Entries 1, 8, and 9). It is also worth noting that
excellent yields of vinyl sulfone 2a, their highly hygroscopic allylsulfone 2h was obtained as a cis alkene, whose stereo-
nature was a major drawback (Table 2, Entries 1 and 4). chemistry was assigned on the basis of its spectroscopic
The ease of handling the alkali metal iodides prompted us
to examine their reactivity (Table 2, Entries 5–7). Both LiI
and NaI gave a mixture of 2a and 3a as can be seen from
the H NMR spectrum of the crude product. To our de-
Table 4. Oxidative sulfonylation of aliphatic alkenes and cyclic
alkene.[a]
1
light, KI gave comparable results to those obtained by using
tetraalkylammonium iodide salts as additives (Table 2, En-
try 7).
On the basis of the results shown in Table 2 (Entry 7),
the optimized reaction conditions were chosen for further
exploration of the substrate scope and the arenesulfinate
sodium salts of this reaction.[32] It was found that most sty-
rene derivatives underwent the reaction to provide the cor-
responding vinyl sulfones in good yields (Table 3). p-Tolu-
enesulfinate and benzenesulfinate sodium salts worked
equally well in this reaction. Moderate yields were observed
for electron-releasing-substituted styrene (Table 3, Entries 6
and 13).
Table 3. Oxidative sulfonylation of styrene derivatives.[a]
Entry
R
Substrate
Ar
Product Yield [%][b]
1
2
3
4
5
6
7
8
C6H5
4-BrC6H4
4-ClC6H4
1a
1b
1c
1d
1e
1f
1g
1a
1b
1c
1d
1e
1f
pTol
pTol
pTol
pTol
pTol
pTol
pTol
Ph
Ph
Ph
Ph
Ph
2a
2b
2c
2d
2e
85
88
86
77
67
48
80
90
87
88
82
82
55
84
2-ClC6H4
4-CH3C6H4
4-CH3OC6H4
4-CH3OCOC6H4
C6H5
2f
2g
2aa
2bb
2cc
2dd
2ee
2ff
2gg
9
4-BrC6H4
4-ClC6H4
2-ClC6H4
10
11
12
13
14
4-CH3C6H4
4-CH3OC6H4
4-CH3OCOC6H4
Ph
Ph
1g
[a] All reactions were performed by using the substrate (0.5 mmol),
pTolSO2Na or PhSO2Na (4 equiv.), PhI(OAc)2 (1.5 equiv.), and KI
(1 equiv.) in CH3CN at room temperature for 1 h. [b] Isolated yield.
The sulfonylation of aliphatic alkenes as well as cyclic
alkenes was also investigated, and the results are summa-
rized in Table 4. Under standard reaction conditions, ali-
phatic alkenes and cyclic alkenes afforded mixtures of vinyl
sulfones and β-iodosulfones as observed by analysis of the
1H NMR spectra of the crude products. Vinyl sulfones
could be obtained by treatment of the crude mixtures with
[a] Reagents and conditions: 1) Alkene (0.5 mmol), pTolSO2Na
(4 equiv.), PhI(OAc)2 (1.5 equiv.), KI (1 equiv.), CH3CN, room
temp., 1 h; 2) DBU, CH3CN, room temp., 30 min. [b] Isolated yield
DBU in CH3CN at room temperature for 30 min. A variety after two steps.
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C. Kuhakarn et al.
FULL PAPER
data (NOE experiments).[33] Finally, cyclic vinylsulfone 2q Table 6. Oxidative β-sulfonylation of α,β-unsaturated carbonyl de-
rivatives and acrylonitrile compounds.[a]
could also be prepared in moderate yield (56%) from cyclo-
hexene.
The methodology works equally well with alkynes
(Table 5). The optimized reaction conditions were applied
to the reaction of arylacetylenes possessing substituents
with different electronic properties on the phenyl rings
(Table 5, Entries 1–4) and 1-octyne (Table 5, Entry 5). Fac-
ile reactions occurred, giving rise to the corresponding β-
iodovinyl sulfones in high yields, each as a single geometri-
cal isomer. On the basis of the spectroscopic data of the β-
iodovinyl sulfone derived from 1-octyne (NOE experi-
ments), the iodine atom was confirmed to be anti to the
sulfonyl group. The stereochemistry of compounds 6a–d
was then assigned on the basis of that of 6e.
Table 5. Sulfonylation of alkynes.[a]
Entry
R
Substrate Product
Yield [%][b]
1
2
3
4
5
C6H5
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
81
86
77
77
64
4-CH3C6H4
4-CH3OC6H4
4-NO2C6H4
CH3(CH2)5
[a] All reactions were performed by using the substrate (0.5 mmol),
pTolSO2Na (4 equiv.), PhI(OAc)2 (1.5 equiv.), and KI (1 equiv.) in
CH3CN at room temperature for 1 h. [b] Isolated yields.
[a] All reactions were performed by using the substrate (0.5 mmol),
pTolSO2Na (4 equiv.), PhI(OAc)2 (1.5 equiv.), and KI (1 equiv.) in
CH3CN at room temperature for 1 h. [b] Isolated yields.
Finally, oxidative β-sulfonylation of α,β-unsaturated car-
bonyl derivatives was investigated, and the results are sum-
marized in Table 6. We found that the optimized conditions
prove to be suitable for a range of alkyl ester derivatives,
and these reactions went smoothly to provide the β-tolu-
enesulfonyl-α,β-unsaturated esters in good yields (62–81%
yield; Table 6, Entries 1–4). A low yield (33%) was observed
with acrylonitrile (Table 6, Entry 5). However, methacry-
lonitrile afforded a mixture of two possible geometrical iso-
mers, which could be separated by column chromatography
[8fa(E)/8fb(Z) = 3:1] in good yields (Table 6, Entry 6). Allyl
methacrylate reacted solely at the electron deficient alkene
moiety to give the corresponding product 8g in moderate
yield (59%; Table 6, Entry 7). Acrylic acid gave no identifi-
able product (Table 6, Entry 8).
performed. When a 1:1 mixture of DIB/KI in CDCl3 was
examined by 1H NMR spectroscopy, a new peak at δ =
2.10 ppm (s) gradually appeared and replaced the acetyl sig-
nal of DIB at δ = 2.02 ppm (s). The new singlet at δ =
2.10 ppm was assigned to acetylhypoiodite (AcOI).[34]
A probable mechanism for the formation of vinyl sul-
fones is outlined in Scheme 1. DIB promotes the oxidation
of the iodide anion, yielding acetylhypoiodite (A) as a puta-
tive intermediate. Subsequent reaction of A with aryl sulfin-
ate gives arylsulfonyl iodide (B), which readily mediates
iodosulfonylation of the alkene.[31] Spontaneous elimination
of HI then takes place when the R group is an aryl or con-
jugated functional group. Aliphatic alkenes require a two-
step reaction involving β-iodosulfonylation followed by
base-induced dehydroiodination. To support our proposed
mechanistic pathway, NMR spectroscopic experiments were Scheme 1. Plausible mechanistic pathway.
5636 Eur. J. Org. Chem. 2010, 5633–5641
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Vinyl Sulfones by PhI(OAc)2/KI-Mediated Reactions of Aryl Sulfinates
(HRMS) were recorded with a Bruker micro TOF spectrometer in
the ESI mode.
Finally, to probe the efficiency and generality of the pres-
ent method against those previously reported utilizing reac-
tive arenesulfonyl iodides prepared in situ by oxidation of
the arenesulfinate sodium salts with oxidizing agents, com-
parative studies were conducted. By following the method
described by Nair et al. employing CAN as an oxidant, it
was found that α,β-unsaturated carbonyl derivatives were
not suitable substrates and vinyl sulfones 8a and 8c were
obtained in 17 and 40% yield, respectively.[9d] The efficiency
of the reaction dramatically depends on the type of solvent
when molecular iodine was employed as the oxidizing rea-
gent. Acetone gave poor results, which is in good agreement
with those described by Julia and co-workers.[9b] When ace-
tonitrile was used as the solvent by employing pTolSO2Na
(4 equiv.) and I2 (1.5 equiv.) at room temperature for 1 h,
styrene derivatives gave β-iodosulfones as major products
along with vinyl sulfones, whereas the reactions of aliphatic
alkenes did not work well and led to recovery of starting
materials in 61–90% yield. In contrast to that reported by
Yus, the reactions of 1a, 1k, and 7a performed in dichloro-
methane by using pTolSO2Na (4 equiv.) and I2 (1.5 equiv.)
at room temperature for 1 h gave the corresponding β-iodo-
sulfones exclusively in good yields. However, an additional
General Procedure A
One-Step Synthesis of Vinyl Sulfones: PhI(OAc)2 (241.6 mg,
0.75 mmol) was added to a suspension of the alkene or alkyne
(0.5 mmol), sodium arenesulfinate (2.0 mmol), and KI (83.0 mg,
0.5 mmol) in CH3CN (2 mL), and the reaction mixture was vigor-
ously stirred at room temperature for 1 h. Upon completion of the
reaction, the reaction mixture was quenched by the addition of a
saturated aqueous solution of Na2S2O3 (5 mL) and basified with a
saturated aqueous solution of NaHCO3 (5 mL). Further stirring
was followed by extraction with EtOAc (3ϫ15 mL). The combined
organic extract was washed with H2O (15 mL) and brine (15 mL),
dried (MgSO4), filtered, and concentrated (aspirator). The residue
was purified by column chromatography.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (2a):[9a] According to gene-
ral procedure A, styrene (1a; 52.0 mg, 0.5 mmol) and sodium p-
toluenesulfinate (356.4 mg, 2.0 mmol) were employed. Column
chromatography (SiO2, 20% EtOAc in hexanes) gave 2a (109.8 mg,
85% yield; white solid, m.p. 118–120 °C, ref.[9a] m.p. 120–121 °C).
1H NMR (300 MHz, CDCl3): δ = 7.85 (d, J = 8.3 Hz, 2 H, ArH),
7.68 (d, J = 15.4 Hz, 1 H, CH), 7.51–7.35 (m, 7 H, ArH), 6.87 (d, J
= 15.4 Hz, 1 H, CH), 2.46 (s, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 144.3, 141.9, 137.8, 132.5, 131.1, 130.3, 129.9, 129.0,
elimination step mediated by base is required to obtain the 128.5, 127.7, 21.6 ppm. IR (KBr): ν˜ = 3046, 2924, 1615, 1595, 1496,
1449, 1315, 1285, 1143, 1086, 973, 810, 748, 665 cm–1. HRMS (ESI-
vinyl sulfones.
TOF): calcd. for C15H14O2SNa [M + Na]+ 281.0612; found
281.0646.
(E)-1-Bromo-4-(2-tosylvinyl)benzene (2b): According to general pro-
cedure A, 4-bromostyrene (1b; 91.9 mg, 0.5 mmol) and sodium p-
toluenesulfinate (356.4 mg, 2.0 mmol) were employed. Column
Conclusions
In conclusion, we have demonstrated the synthetic appli-
cation of (diacetoxyiodo)benzene (DIB)/KI to promote the
chromatography (SiO2, 20% EtOAc in hexanes) gave 2b (148.4 mg,
reaction of sodium arenesulfinates with alkenes and al- 88% yield; white solid, m.p. 163–164 °C). 1H NMR (300 MHz,
CDCl3): δ = 7.75 (d, J = 8.1 Hz, 2 H, ArH), 7.51 (d, J = 15.4 Hz,
1 H, CH), 7.44 (d, J = 8.4 Hz, 2 H, ArH), 7.29–7.24 (m, 4 H, ArH),
6.78 (d, J = 15.4 Hz, 1 H, CH), 2.36 (s, 3 H, CH3) ppm. 13C NMR
(75 MHz, CDCl3): δ = 144.5, 140.5, 137.5, 132.3, 131.4, 130.0,
kynes. The method is simple and be conducted in one pot
under non-anhydrous conditions and tolerates a variety of
functional groups. The results, in many aspects, are superior
to those previously reported. In view of the experimental
simplicity and the mild reaction conditions, the present
method is an important alternative to existing methods for
the synthesis of vinyl sulfones and β-iodovinyl sulfones,
which are an important class of compounds in organic
chemistry.
129.8, 128.4, 127.7, 125.5, 21.6 ppm. IR (KBr): ν = 3053, 1614,
˜
1583, 1482, 1303, 1287, 1142, 1084, 1068, 1008, 861, 785, 671 cm–1.
HRMS (ESI-TOF): calcd. for C15H13BrO2SNa [M
358.9717; found 358.9708.
+
Na]+
(E)-[2-(Phenylsulfonyl)vinyl]benzene (2aa):[35] According to general
procedure A, styrene (1a; 52.0 mg, 0.5 mmol) and sodium benzene-
sulfinate (328.4 mg, 2.0 mmol) were employed. Column chromatog-
raphy (SiO2, 20% EtOAc in hexanes) gave 2aa (109.9 mg, 90%
1
yield; white solid, m.p. 68–70 °C, ref.[35] m.p. 75–76 °C). H NMR
Experimental Section
(300 MHz, CDCl3): δ = 7.99–7.96 (m, 2 H, ArH), 7.69 (d, J =
15.4 Hz, 1 H, CH), 7.64–7.34 (m, 8 H, ArH), 6.89 (d, J = 15.4 Hz,
1 H, CH) ppm. 13C NMR (75 MHz, CDCl3): δ = 142.5, 140.8,
133.3, 132.4, 131.2, 129.3, 129.1, 128.5, 127.6, 127.3 ppm. IR
General Remarks: All reagents were obtained from commercial
sources and used without further purification. Thin-layer
chromatography was carried out on TLC alumina sheets with silica
gel 60 F254 (Merck). Chromatographic purification of products
was accomplished by using column chromatography on silica gel
with hexanes/EtOAc as eluent and all solid compounds were recrys-
tallized from hexanes/CH2Cl2. Melting points were recorded with
a digital Electrothermal Melting 9100 apparatus. 1H NMR spectra
were recorded with a Bruker DPX-300 (300 MHz), Bruker Avance-
300 (300 MHz), or Bruker Avance-500 (500 MHz) spectrometer in
CDCl3 by using tetramethylsilane (δ = 0 ppm) as an internal stan-
dard. 13C NMR spectra were recorded with a Bruker Avance-300
(75 MHz) spectrometer by using tetramethylsilane as an internal
standard. Infrared spectra were recorded with a Perkin–Elmer 683
GX FTIR System spectrometer. High-resolution mass spectra
(KBr): ν = 3056, 1612, 1576, 1496, 1448, 1301, 1177, 1146, 1086,
˜
972, 856, 818, 743, 690 cm–1. HRMS (ESI-TOF): calcd. for
C14H12O2SNa [M + Na]+ 267.0456; found 267.0439.
(E)-1-Bromo-4-[2-(phenylsulfonyl)vinyl]benzene (2bb): According to
general procedure A, 4-bromostyrene (1b; 91.9 mg, 0.5 mmol) and
sodium benzenesulfinate (328.4 mg, 2.0 mmol) were employed.
Column chromatography (SiO2, 20% EtOAc in hexanes) gave 2bb
(140.6 mg, 87% yield; white solid, m.p. 152–154 °C). 1H NMR
(300 MHz, CDCl3): δ = 7.96 (d, J = 7.4 Hz, 2 H, ArH), 7.65–7.48
(m, 6 H, ArH, CH), 7.34 (d, J = 8.6 Hz, 2 H, ArH), 6.91 (d, J =
15.5 Hz, 1 H, CH) ppm. 13C NMR (75 MHz, CDCl3): δ = 141.0,
Eur. J. Org. Chem. 2010, 5633–5641
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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C. Kuhakarn et al.
FULL PAPER
140.5, 133.5, 132.4, 131.3, 129.9, 129.4, 128.1, 127.7, 125.5 ppm.
colorless viscous liquid). 1H NMR (300 MHz, CDCl3): δ = 7.78 (d,
J = 8.3 Hz, 2 H, ArH), 7.37 (d, J = 8.0 Hz, 2 H, ArH), 7.31 (d, J
= 15.1 Hz, 1 H, CH), 6.79 (d, J = 15.1 Hz, 1 H, CH), 4.17 (t, J =
6.6 Hz, 2 H, CH2), 2.44 (s, 3 H, CH3), 1.63 (quint., J = 6.6 Hz, 2
H, CH2), 1.40–1.33 (m, 2 H, CH2), 0.91 (t, J = 7.3 Hz, 3 H,
CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 163.4, 145.5, 143.3,
135.4, 130.4, 130.1, 128.2, 65.7, 30.3, 21.5, 18.9, 13.4 ppm. IR
IR (KBr): ν = 3056, 1619, 1583, 1485, 1446, 1398, 1308, 1285, 1153,
˜
1085, 1068, 1008, 976, 856, 784 cm–1. HRMS (ESI-TOF): calcd.
for C14H11O2SBrNa [M + Na]+ 344.9561; found 344.9577.
(E)-1-Chloro-2-[2-(phenylsulfonyl)vinyl]benzene (2dd): According to
general procedure A, 2-chlorostyrene (1d; 69.3 mg, 0.5 mmol) and
sodium benzenesulfinate (328.4 mg, 2.0 mmol) were employed.
Column chromatography (SiO2, 10% EtOAc in hexanes) gave 2dd
(114.3 mg, 82% yield; pale-yellow solid, m.p. 98–100 °C). 1H NMR
(300 MHz, CDCl3): δ = 8.08 (d, J = 15.4 Hz, 1 H, CH), 7.98–7.95
(m, 2 H, ArH), 7.66–7.49 (m, 4 H, ArH), 7.42–7.25 (m, 3 H, ArH),
6.93 (d, J = 15.4 Hz, 1 H, CH) ppm. 13C NMR (75 MHz, CDCl3):
δ = 140.4, 138.4, 135.3, 133.5, 131.9, 130.7, 130.4, 130.1, 129.4,
(neat): ν = 3064, 2962, 2875, 1732, 1596, 1494, 1464, 1385, 1327,
˜
1297, 1228, 1167, 1148, 1087, 963, 812, 708, 644 cm–1. HRMS (ESI-
TOF): calcd. for C14H18O4SNa [M + Na]+ 305.0823; found
305.0772.
(E)-tert-Butyl 3-Tosylacrylate (8d): According to general pro-
cedure A, tert-butyl acrylate (7d; 56.1 mg, 0.5 mmol) and sodium
p-toluenesulfinate (356.4 mg, 2.0 mmol) were employed. Column
chromatography (SiO2, 15% EtOAc in hexanes) gave 8d (87.5 mg,
62% yield; white solid, m.p. 95–97 °C). 1H NMR (300 MHz,
CDCl3): δ = 7.81 (d, J = 8.3 Hz, 2 H, ArH), 7.39 (d, J = 8.0 Hz, 2
H, ArH), 7.23 (d, J = 15.1 Hz, 1 H, CH), 6.73 (d, J = 15.1 Hz, 1
H, CH), 2.48 (s, 3 H, CH3), 1.49 (s, 9 H, 3 CH3) ppm. 13C NMR
(75 MHz, CDCl3): δ = 162.6, 145.4, 142.5, 135.7, 132.4, 130.2,
128.4, 127.8, 127.2 ppm. IR (KBr): ν = 3051, 1607, 1591, 1470,
˜
1448, 1304, 1201, 1148, 1086, 1042, 971, 824, 747, 689 cm–1. HRMS
(ESI-TOF): calcd. for C14H11O2SClNa [M + Na]+ 301.0066; found
301.0059.
(E)-1-Methoxy-4-[2-(phenylsulfonyl)vinyl]benzene (2ff): According
to general procedure A, 4-methoxystyrene (1f; 67.1 mg, 0.5 mmol)
and sodium benzenesulfinate (328.4 mg, 2.0 mmol) were employed.
Column chromatography (SiO2, 20% EtOAc in hexanes) gave 2ff
(75.4 mg, 55% yield; white solid, m.p. 74–77 °C). 1H NMR
(300 MHz, CDCl3): δ = 7.86–7.83 (m, 2 H, ArH), 7.54 (d, J =
15.4 Hz, 1 H, CH), 7.50–7.40 (m, 3 H, ArH), 7.33 (d, J = 8.8 Hz,
2 H, ArH), 6.79 (d, J = 8.5 Hz, 2 H, ArH), 6.64 (d, J = 15.4 Hz,
1 H, CH), 3.71 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ
= 162.1, 142.3, 141.2, 133.1, 130.3, 129.2, 127.5, 125.0, 124.5, 114.5,
128.3, 83.0, 27.9, 21.6 ppm. IR (KBr): ν = 3070, 3039, 2986, 2967,
˜
1713, 1625, 1595, 1480, 1393, 1368, 1311, 1249, 1156, 1087, 984,
828, 807, 720, 645 cm–1. HRMS (ESI-TOF): calcd. for
C14H18O4SNa [M + Na]+ 305.0823; found 305.0859.
(E)-2-Methyl-3-tosylacrylonitrile (8fa) and (Z)-2-Methyl-3-tosyl-
acrylonitrile (8fb): According to general procedure A, methacrylo-
nitrile (7f; 33.6 mg, 0.5 mmol) and sodium p-toluenesulfinate
(356.4 mg, 2.0 mmol) were employed. Column chromatography
(SiO2, 10–20% EtOAc in hexanes) gave 8fa and 8fb. Data for 8fa:
Colorless solid (58.6 mg, 53% yield), m.p. 93–94 °C. 1H NMR
(300 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H, ArH), 7.43 (d, J
= 8.0 Hz, 2 H, ArH), 6.89 (q, J = 1.6 Hz, 1 H, CH), 2.50 (s, 3 H,
CH3), 2.42 (d, J = 1.6 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 146.0, 143.1, 136.8, 130.4, 127.9, 123.2, 117.1, 21.6,
55.4 ppm. IR (KBr): ν = 3054, 2991, 2835, 1603, 1573, 1512, 1447,
˜
1422, 1306, 1287, 1262, 1173, 1145, 1082, 1038, 979, 867, 803, 752,
685 cm–1. HRMS (ESI-TOF): calcd. for C15H14O3SNa [M + Na]+
297.0561; found 297.0563.
(E)-1-[2-Iodo-2-(4-nitrophenyl)vinylsulfonyl]-4-methylbenzene (6d):
According to general procedure A, 4-ethynylnitrobenzene (5d;
73.6 mg, 0.5 mmol) and sodium p-toluenesulfinate (356.4 mg,
2.0 mmol) were employed. Column chromatography (SiO2, 20%
EtOAc in hexanes) gave 6d (165.3 mg, 77% yield; pale-yellow solid,
16.4 ppm. IR (KBr): ν = 3038, 2924, 2233, 1619, 1594, 1440, 1383,
˜
1329, 1299, 1182, 1149, 1087, 1040, 856, 811, 670 cm–1. HRMS
(ESI-TOF): calcd. for C11H11NO2SNa [M + Na]+ 244.0408; found
244.0381. Data for 8fb: Colorless solid (19.9 mg, 18% yield), m.p.
112–114 °C. 1H NMR (300 MHz, CDCl3): δ = 7.88 (d, J = 8.4 Hz,
2 H, ArH), 7.41 (d, J = 8.0 Hz, 2 H, ArH), 6.87 (q, J = 1.6 Hz, 1
H, CH), 2.47 (s, 3 H, CH3), 2.16 (d, J = 1.6 Hz, 3 H, CH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 145.9, 142.9, 135.9, 130.2, 128.2,
1
m.p. 186–189 °C). H NMR (300 MHz, CDCl3): δ = 8.12 (d, J =
8.8 Hz, 2 H, ArH), 7.48 (d, J = 8.1 Hz, 2 H, ArH), 7.35 (d, J =
8.8 Hz, 2 H, ArH), 7.31 (s, 1 H, CH), 7.21 (d, J = 8.1 Hz, 2 H,
ArH), 2.36 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
148.1, 145.9, 145.4, 142.5, 136.8, 130.1, 128.5, 127.8, 123.2, 109.1,
21.6 ppm. IR (KBr): ν = 3077, 3041, 1602, 1583, 1519, 1345, 1321,
˜
1290, 1145, 1082, 1016, 886, 845, 817, 761, 653 cm–1. HRMS (ESI-
TOF): calcd. for C15H12INO4SNa [M + Na]+ 451.9429; found
451.9456.
121.1, 114.2, 22.3, 21.6 ppm. IR (KBr): ν = 3038, 2924, 2233, 1619,
˜
1594, 1441, 1384, 1329, 1307, 1299, 1182, 1149, 1087, 1041, 857,
812, 670 cm–1. HRMS (ESI-TOF): calcd. for C11H11NO2SNa [M
+ Na]+ 244.0408; found 244.0376.
(E)-Methyl 2-Methyl-3-tosylacrylate (8b): According to general
procedure A, methyl methacrylate (7b; 50.0 mg, 0.5 mmol) and so-
dium p-toluenesulfinate (356.4 mg, 2.0 mmol) were employed. Col-
umn chromatography (SiO2, 15% EtOAc in hexanes) gave 8b
(103.0 mg, 81% yield; colorless solid, m.p. 53–56 °C). 1H NMR
(300 MHz, CDCl3): δ = 7.81 (d, J = 8.3 Hz, 2 H, ArH), 7.37 (d, J
= 8.4 Hz, 2 H, ArH), 7.22 (q, J = 1.5 Hz, 1 H, CH), 3.77 (s, 3 H,
CH3), 2.45 (s, 3 H, CH3), 2.32 (d, J = 1.5 Hz, 3 H, CH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 166.0, 145.1, 140.5, 137.6, 137.6,
(E)-Allyl 2-Methyl-3-tosylacrylate (8g): According to general pro-
cedure A, allyl methacrylate (7g; 63.1 mg, 0.5 mmol) and sodium
p-toluenesulfinate (356.4 mg, 2.0 mmol) were employed. Column
chromatography (SiO2, 10–15% EtOAc in hexanes) gave 8g
(82.7 mg, 59% yield; colorless viscous liquid). 1H NMR (300 MHz,
CDCl3): δ = 7.82 (d, J = 8.3 Hz, 2 H, ArH), 7.38 (d, J = 8.4 Hz, 2
H, ArH), 7.25 (d, J = 1.5 Hz, 1 H, CH), 5.95–5.84 (m, 1 H, CH),
5.33 (dd, J = 17.3, 1.3 Hz, 1 H, CH), 5.27 (dd, J = 11.6, 1.3 Hz, 1
H, CH), 4.66 (d, J = 5.9 Hz, 2 H, CH2), 2.46 (s, 3 H, CH3), 2.34
(d, J = 1.5 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
165.2, 145.1, 140.7, 137.7, 137.5, 131.1, 130.0, 127.6, 119.2, 66.6,
130.0, 127.6, 52.9, 21.5, 13.2 ppm. IR (KBr): ν = 3048, 2959, 1717,
˜
1630, 1596, 1490, 1437, 1381, 1312, 1267, 1182, 1145, 1088, 973,
857, 817, 737 cm–1. HRMS (ESI-TOF): calcd. for C12H14O4SNa
[M + Na]+ 277.0510; found 277.0459.
(E)-Butyl 3-Tosylacrylate (8c): According to general procedure A,
n-butyl acrylate (7c; 56.1 mg, 0.5 mmol) and sodium p-toluenesulf-
inate (356.4 mg, 2.0 mmol) were employed. Column chromatog-
raphy (SiO2, 10% EtOAc in hexanes) gave 8c (110.1 mg, 78% yield;
21.5, 13.2 ppm. IR (neat): ν = 3054, 2953, 1727, 1626, 1597, 1494,
˜
1447, 1382, 1362, 1324, 1232, 1151, 1117, 1086, 997, 941, 817, 782,
708 cm–1. HRMS (ESI-TOF): calcd. for C14H16O4SNa [M + Na]+
303.0667; found 303.0613.
5638
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 5633–5641

Vinyl Sulfones by PhI(OAc)2/KI-Mediated Reactions of Aryl Sulfinates
General Procedure B
814, 660 cm–1. HRMS (ESI-TOF): calcd. for C12H15O2SBrNa [M
+ Na]+ 324.9874; found 324.9898.
Two-Step Synthesis of Vinyl Sulfones: PhI(OAc)2 (241.6 mg,
0.75 mmol) was added to a suspension of alkene (0.5 mmol), p-
toluenesulfinate (356.4 mg, 2.0 mmol), and KI (83.0 mg, 0.5 mmol)
in CH3CN (2 mL), and the reaction mixture was vigorously stirred
at room temperature for 1 h. The reaction mixture was quenched
by the addition of a saturated aqueous solution of Na2S2O3 (5 mL)
and basified with a saturated aqueous solution of NaHCO3 (5 mL).
Further stirring was followed by extraction with EtOAc
(3ϫ15 mL). The combined organic extract was washed with H2O
(15 mL) and brine (15 mL), dried (MgSO4), filtered, and concen-
(E)-11-Tosylundec-10-enal (2m): According to general procedure B,
undec-10-enal (1m; 84.1 mg, 0.5 mmol) was employed. Column
chromatography (SiO2, 15% EtOAc in hexanes) gave 2m (129.0 mg,
1
80% yield; colorless viscous liquid). H NMR (300 MHz, CDCl3):
δ = 9.75 (t, J = 1.8 Hz, 1 H, CHO), 7.74 (d, J = 8.3 Hz, 2 H, ArH),
7.32 (d, J = 8.5 Hz, 2 H, ArH), 6.94 (dt, J = 15.1, 6.8 Hz, 1 H,
CH), 6.30 (d, J = 15.1 Hz, 1 H, CH), 2.44–2.38 (m, 5 H, CH3,
CH2), 2.26–2.17 (m, 2 H, CH2), 1.60–1.20 [m, 12 H, (CH2)6] ppm.
13C NMR (75 MHz, CDCl3): δ = 202.7, 146.4, 144.0, 137.8, 130.6,
129.7, 127.5, 43.7, 31.3, 29.0, 28.9, 28.8, 27.4, 21.9, 21.4 ppm. IR
1
trated (aspirator). H NMR spectroscopy of the crude mixture re-
(neat): ν = 3048, 2929, 2856, 1712, 1634, 1597, 1495, 1456, 1403,
˜
vealed that it was mixture of β-iodosulfone and vinyl sulfone. With-
out purification, the crude mixture was diluted with CH3CN
(2 mL), and to this solution was added 1,8-diazabicyclo[5.4.0]un-
dec-7-ene (DBU; 76.1 mg, 0.5 mmol). The reaction mixture was
vigorously stirred at room temperature for 30 min before it was
quenched with a saturated aqueous solution of NaHCO3 (5 mL).
Further stirring was followed by extraction with EtOAc
(2ϫ15 mL). The combined organic extract was washed with H2O
(15 mL) and brine (15 mL), dried (MgSO4), filtered, and concen-
trated (aspirator). The residue was purified by column chromatog-
raphy.
1317, 1303, 1287, 1144, 1087, 970, 814, 660 cm–1. HRMS (ESI-
TOF): calcd. for C18H26O3SNa [M + Na]+ 345.1500; found
345.1558.
(E)-2-(10-Tosyldec-9-enyl)-1,3-dioxane (2n): According to general
procedure B, 2-(dec-9-enyl)-1,3-dioxane (1n; 113.2 mg, 0.5 mmol)
was employed. Column chromatography (SiO2, 15% EtOAc in hex-
anes) gave 2n (154.1 mg, 81% yield; colorless solid, m.p. 81–83 °C).
1H NMR (300 MHz, CDCl3): δ = 7.76 (d, J = 8.3 Hz, 2 H, ArH),
7.33 (d, J = 8.1 Hz, 2 H, ArH), 6.95 (dt, J = 15.1, 6.8 Hz, 1 H,
CH), 6.29 (d, J = 15.1 Hz, 1 H, CH), 4.51 (t, J = 5.1 Hz, 1 H, CH),
4.13–4.08 (m, 2 H, 2 CH of OCH2), 3.81–3.72 (m, 2 H, 2 CH of
OCH2), 2.44 (s, 3 H, CH3), 2.25–2.18 (m, 2 H, CH2), 2.10–2.05 (m,
1 H, CH of CH2), 1.61–1.54 (m, 2 H, CH2), 1.44–1.26 [m, 13 H,
CH of CH2, (CH2)6] ppm. 13C NMR (75 MHz, CDCl3): δ = 146.5,
144.0, 137.8, 130.5, 129.7, 127.5, 102.3, 66.8, 35.1, 31.3, 29.2, 29.1,
(Z)-1-Methyl-4-[3-(phenoxy)allylsulfonyl]benzene (2h): According to
general procedure B, allyl phenyl ether (1h; 67.1 mg, 0.5 mmol) was
employed. Column chromatography (SiO2, 15% EtOAc in hexanes)
gave 2h (100.9 mg, 70% yield; colorless solid, m.p. 83–85 °C). 1H
NMR (300 MHz, CDCl3): δ = 7.81 (d, J = 8.2 Hz, 2 H, ArH),
7.29–7.22 (m, 4 H, ArH), 7.09–7.04 (m, 1 H, ArH), 6.66 (d, J =
7.5 Hz, 2 H, ArH), 6.51 (d, J = 6.0 Hz, 1 H, CH), 4.92 (td, J =
8.0, 6.0 Hz, 1 H, CH), 4.07 (d, J = 8.0 Hz, 2 H, CH2), 2.37 (s, 3
H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 156.4, 146.4,
144.4, 135.6, 129.5, 129.4, 128.6, 123.5, 116.5, 97.8, 52.6, 21.6 ppm.
29.0, 28.9, 27.5, 25.8, 23.8, 21.5 ppm. IR (KBr): ν = 3055, 2934,
˜
2857, 1632, 1597, 1492, 1450, 1410, 1334, 1301, 1287, 1244, 1147,
1117, 1098, 1085, 986, 968, 890, 742, 668 cm–1. HRMS (ESI-TOF):
calcd. for C21H32O4SNa [M + Na]+ 403.1919; found 403.1949.
(E)-1-Methoxy-4-(3-tosylprop-1-enyl)benzene (4p): According to ge-
neral procedure B, allyl anisole (1p; 74.1 mg, 0.5 mmol) was em-
ployed. Column chromatography (SiO2, 10–20% EtOAc in hex-
anes) gave products 2p (16.6 mg, 11% yield) and 4p (95.3 mg, 63%
yield). Data for 4p: Brownish solid, m.p. 117–119 °C. 1H NMR
(300 MHz, CDCl3): δ = 7.66 (d, J = 8.2 Hz, 2 H, ArH), 7.23 (d, J
= 8.0 Hz, 2 H, ArH), 7.14 (d, J = 8.7 Hz, 2 H, ArH), 6.75 (d, J =
8.6 Hz, 2 H, ArH), 6.24 (d, J = 15.8 Hz, 1 H, CH), 5.86 (dt, J =
15.8, 7.6 Hz, 1 H, CH), 3.82 (d, J = 7.6 Hz, 2 H, CH2), 3.71 (s, 3
H, CH3), 2.33 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ
= 159.8, 144.6, 138.4, 135.6, 129.6, 128.6, 128.4, 127.8, 114.0, 112.7,
IR (KBr): ν = 3063, 2976, 1670, 1592, 1486, 1406, 1385, 1312, 1302,
˜
1266, 1209, 1143, 1080, 983, 770, 742 cm–1. HRMS (ESI-TOF):
calcd. for C16H16O3SNa [M + Na]+ 311.0718; found 311.0759.
(E)-1-Methyl-4-(5-phenoxypent-1-enylsulfonyl)benzene (2i): Accord-
ing to general procedure B, 4-pentenyl phenyl ether (1i; 81.1 mg,
0.5 mmol) was employed. Column chromatography (SiO2, 20%
EtOAc in hexanes) gave 2i (132.9 mg, 84% yield; white solid, m.p.
1
73–75 °C). H NMR (300 MHz, CDCl3): δ = 7.74 (d, J = 8.3 Hz,
2 H, ArH), 7.32–7.22 (m, 4 H, ArH), 7.05–6.91 (m, 2 H, ArH,
CH), 6.84–6.81 (m, 2 H, ArH), 6.35 (d, J = 15.1 Hz, 1 H, CH),
3.94 (t, J = 6.1 Hz, 2 H, CH2), 2.48–2.41 (m, 5 H, CH3, CH2),
1.98–1.89 (m, 2 H, CH2) ppm. 13C NMR (75 MHz, CDCl3): δ =
158.6, 145.3, 144.2, 137.7, 131.4, 129.8, 129.4, 127.6, 120.8, 114.4,
60.5, 55.2, 21.5 ppm. IR (KBr): ν = 3033, 2969, 2915, 1644, 1605,
˜
1575, 1512, 1463, 1400, 1313, 1289, 1252, 1177, 1145, 1087, 978,
819, 733, 664 cm–1. HRMS (ESI-TOF): calcd. for C17H18O3SNa
[M + Na]+ 325.0874; found 325.0860.
66.4, 28.2, 27.4, 21.5 ppm. IR (KBr): ν = 3039, 2961, 2873, 1634,
˜
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures and spectroscopic data; NOE inter-
actions of 2h, 6e, and 8fa/8fb; copies of the 1H and 13C NMR
spectra of all compounds.
1601, 1586, 1492, 1469, 1441, 1397, 1315, 1307, 1279, 1242, 1178,
1083, 1042, 979, 811, 761 cm–1. HRMS (ESI-TOF): calcd. for
C18H20O3SNa [M + Na]+ 339.1031; found 339.1055.
(E)-1-(5-Bromopent-1-enylsulfonyl)-4-methylbenzene (2k): Accord-
ing to general procedure B, 5-bromopentene (1k; 74.5 mg,
0.5 mmol) was employed. Column chromatography (SiO2, 15%
EtOAc in hexanes) gave 2k (121.3 mg, 80% yield; colorless oil). 1H
Acknowledgments
NMR (300 MHz, CDCl3): δ = 7.67 (d, J = 8.2 Hz, 2 H, ArH), 7.26 Financial support from the Thailand Research Fund and the Com-
(d, J = 8.0 Hz, 2 H, ArH), 6.84 (dt, J = 15.1, 6.8 Hz, 1 H, CH), mission on Higher Education (RMU5180040), the Center for Inno-
6.30 (d, J = 15.1 Hz, 1 H, CH), 3.31 (t, J = 6.3 Hz, 2 H, CH2),
vation in Chemistry (PERCH-CIC), the Development and Pro-
2.36–2.30 (m, 5 H, CH3, CH2), 1.93 (quint., J = 6.8 Hz, 2 H, motion of Science and Technology Talent Project (DPST), the In-
CH2) ppm. 13C NMR (75 MHz, CDCl3): δ = 144.3, 143.9, 137.4,
stitute for the Promotion of Teaching Science and Technology, and
the Commission on Higher Education (CHE-RES-RG), Ministry
of Education is gratefully acknowledged.
131.9, 129.8, 127.5, 32.1, 30.3, 29.6, 21.5 ppm. IR (neat): ν = 3047,
˜
2925, 1627, 1597, 1495, 1441, 1317, 1302, 1289, 1145, 1087, 961,
Eur. J. Org. Chem. 2010, 5633–5641
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5639

C. Kuhakarn et al.
FULL PAPER
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Published Online: August 24, 2010
Eur. J. Org. Chem. 2010, 5633–5641
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5641