Safe and Metal-Free Synthesis of 1-Alkenyl Aryl Sulfides and Their Sulfones from Thiiranes and Diaryliodonium Salts

Article abstract of DOI:10.1055/s-0036-1591559

A series of 1-alkenyl aryl sulfides was synthesized from thiiranes and diaryliodonium salts in tetrahydrofuran in the presence of potassium tert -butoxide. The proposed reaction mechanism involves generation of benzynes from the diaryliodonium salts in the presence of the base. Then, nucleophilic attack of the benzynes by thiiranes, followed by hydrogen abstraction and ring opening of the generated thiiranium intermediates, provides the sulfides. These sulfides were further oxidized with performic acid to the corresponding sulfones. The current method provides a metal-free and safe method for the preparation of 1-alkenyl aryl sulfides and their sulfones.

Full text of DOI:10.1055/s-0036-1591559

SYNTHESIS
0
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9
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8
8
1
1
4
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1
0
X
© Georg Thieme Verlag Stuttgart · New York
2018, 50, A–I
paper
A
en
J. Dong, J. Xu
Paper
Synthesis
Safe and Metal-Free Synthesis of 1-Alkenyl Aryl Sulfides and Their
Sulfones from Thiiranes and Diaryliodonium Salts
Jun Dong
Jiaxi Xu*
R2
R2
S
KOtBu, THF
H2O2
R1
Ar
Ar2I+X–
R1
39–82%
+
S
R2
SAr
HCO2H
R1
20 °C, 4 h
O
O
State Key Laboratory of Chemical Resource Engineering,
Department of Organic Chemistry, Faculty of Science,
Beijing University of Chemical Technology, Beijing
100029, P. R. of China
36–69% (two steps)
Ar, Ar = Ph, Ph; Ph, 4-BrC6H4; 4-BrC6H4, 4-BrC6H4; Ph, 4-MeC6H4; Ph, 2-Naph
–
X–
=
Cl–, BF4–, PF6
R1 = Ph, 2/3/4-MeC6H4, 4-MeOC6H4, 4-BrC6H4, 4-ClC6H4, 4-CF3C6H4, Bu, R2 = H;
R1 = R2 = H; R1–R2 = (CH2)4
jxxu@mail.buct.edu.cn
Received: 22.01.2018
Accepted after revision: 05.03.2018
Published online: 04.04.2018
arylthiomethylphosphonates and aromatic aldehydes,17 5)
the reaction of (arylthio)carbenes and nitrile anions,18 6)
the palladium-catalyzed reaction of 1,3-oxathiolanes and
aryl bromides,19 and 7) the reaction of benzyne (generated
from 2-aminobenzoate) and thiiranes20 (Scheme 1).
Thiiranes are important organic synthetic intermedi-
ates.21 During recent years, our research group has been in-
terested in the application of thiiranes in the preparation of
sulfur-containing compounds via ring-opening and expan-
sion reactions.22,23 Diaryliodonium halides are readily avail-
able chemicals,24 and have been verified experimentally to
generate arynes.25 However, they have seldom been applied
as safe benzyne precursors in the presence of base.26
DOI: 10.1055/s-0036-1591559; Art ID: ss-2018-h0042-op
Abstract A series of 1-alkenyl aryl sulfides was synthesized from
thiiranes and diaryliodonium salts in tetrahydrofuran in the presence of
potassium tert-butoxide. The proposed reaction mechanism involves
generation of benzynes from the diaryliodonium salts in the presence
of the base. Then, nucleophilic attack of the benzynes by thiiranes, fol-
lowed by hydrogen abstraction and ring opening of the generated
thiiranium intermediates, provides the sulfides. These sulfides were fur-
ther oxidized with performic acid to the corresponding sulfones. The
current method provides a metal-free and safe method for the prepara-
tion of 1-alkenyl aryl sulfides and their sulfones.
Key words benzynes, diaryliodonium salts, sulfides, sulfones,
Hoshino and co-workers already reported the efficient
synthesis of alkenyl aryl sulfides using thiiranes and ben-
zyne with 2-carboxybenzenediazonium as a benzyne pre-
cursor in 1984.20 In addition, base-promoted benzyne for-
mation from diaryliodonium salts was reported in 2016 by
the Huangs groups.26 However, the reactions of diaryliodo-
nium salts with thiiranes, or even with other three-mem-
bered heterocycles, have not been explored. On the other
hand, in the presence of base, thiiranes may undergo nucle-
ophilic ring-opening reactions,21,22 a competitive reaction
with base-promoted benzyne formation from diaryliodoni-
um salts. Thus, it is valuable to explore the reaction of di-
aryliodonium salts and thiiranes in the presence of base.
Furthermore, in Hoshino’s work,20 only benzyne itself was
investigated. In our current work, we have attempted the
reaction of substituted benzynes, generated from symmet-
ric and unsymmetric bis(substituted phenyl)iodonium
salts, with thiiranes and discuss the chemo- and regioselec-
tivities. Notably, diaryliodonium salts are more easily pre-
pared than substituted 2-carboxybenzenediazoniums.
More and detailed information on the reaction of thiiranes
and diaryliodonium salts are provided. Thus, we herein
thiiranes, ring opening
Alkenyl aryl sulfides and sulfones are present in many
biologically active compounds.1 They are also useful syn-
thetic intermediates in organic transformations,2 including
enol substitutions,3 Diels–Alder cycloadditions,4 [2+2] cyc-
loadditions,5 thio-Claisen rearrangements,6 as Michael ac-
ceptors,7 or in olefin metathesis.8 Thus, the preparation of
1-alkenyl aryl sulfides has received great attention during
recent decades. The main synthetic strategies for 1-alkenyl
aryl sulfides include 1) the transition-metal-catalyzed hy-
drothiolation of terminal alkynes with thiophenols9 or aryl
disulfides10 with different regioselectivities, and the organ-
ic ionic base and Brønsted acid catalyzed hydrothiolation of
terminal alkynes with sulfonyl hydrazides,11 and 2) the
transition-metal-catalyzed coupling of 1-alkenyl halides
with thiophenols,12 sodium benzenethiolate,13 or aryl disul-
fides14 (Scheme 1). Alternatively, other synthetic methods
have been reported, such as 3) the acid/phosphide-induced
arenethiyl radical addition to alkynes,15 and the amine-in-
duced reductive addition of arenethiyl radical to alkynes,16
4) the Horner–Wittig reaction of bis(2,2,2-trifluoroethyl)
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

B
J. Dong, J. Xu
Paper
Synthesis
that it is more suitable to conduct the reaction at 20 °C.
Thus, further optimizations were conducted at 20 °C. Dif-
ferent bases, K2CO3 and Na2CO3·2 H2O, were evaluated
which proved completely inefficient for the transformation
(Table 1, entries 7 and 8). NaOtBu showed a lower efficiency
than KOtBu, producing 3a in 68% yield (Table 1, entry 9).
Prolonging the reaction time to 6 hours resulted in a de-
creased yield, to 59% (Table 1, entry 10). Increasing the
amount of KOtBu from 0.375 mmol to 0.40 mmol improved
the yield slightly (from 70% to 71%) (Table 1, entry 11). Fur-
ther increase of the base to 0.425 mmol resulted in a weak-
ly decreased yield (from 70% to 68%) (Table 1, entry 12). Two
other diphenyliodonium salts, diphenyliodonium tetrafluo-
Previous methods
1) Hydrothiolation of alkynes with arenethiols,
arenethiolates, and aryl disulfides
R
ArSH
MLn
R
SAr
+
+
SAr
R
SAr
ArSSAr
R
+
[DBU][HOAc]/HOAc
MW, 120 °C, 5 min
R
ArSO2NHNH2
SAr
2) Cross coupling of alkenyl halides with arenethiols,
arenethiolates, and aryl disulfides
ArSH
MLn
R
R
ArSNa
+
SAr
X
ArSSAr
–
roborate (Ph2I+BF4 ) (2b) and diphenyliodonium hexafluo-
3) Arenethiyl radical addition to alkynes
–
rophosphate (Ph2I+PF6 ) (2c), were used instead of chloride
acid/Ph3P/H2O
ArSO2Na
R
2a; however, both showed lower efficiencies than 2a (Table
1, entries 13 and 14).27 Finally, the optimal conditions were
established as KOtBu (0.40 mmol) at 20 °C for 4 hours (Table
1, entry 11). Only trace amounts (<3%) of phenyl cis-styryl
R
amine
ArS·
SAr
ArSSAr
4) Horner–Wittig reaction of arylthiomethylphosphonates and aldehydes
KHMDS, –78 °C
or NaH, r.t., THF
O
1
OCH2CF3
OCH2CF3
sulfide (cis-3a) were observed on H NMR analysis of the
Ar'
Ar'S
P
+
ArCHO
SAr
reaction mixture in each case. The cis-isomer displays a
larger coupling constant between its two vicinal olefinic
hydrogens than the corresponding trans-isomer.
5) Reaction of (arylthio)carbenes and nitrile anions
LinBu, THF
Cl
R1
R2CH2CN
+
R2
ArS
R1
–85 to –30 °C
SAr
6) Reaction of 1,3-oxathiolanes and aryl bromides
Table 1 Optimization of the Reaction of Phenylthiirane (1a) with
Diphenyliodonium Chloride (2a)a
1.5 mol% Xantphos G3
3 equiv KOtBu, CPME, 70 °C, 22 h
S
ArBr
+
SAr
O
S
base, THF
Ph
Ph2I+Cl–
+
7) Reaction of benzyne and thiiranes
SPh
Ph
S
3a
+
2a
1a
N2
R2
R1
R2
R1
Entry Ph2I+X–
Base (mmol)
Temp (°C)
Time Yieldb (%)
–
SPh
CO2
(h)
Current method
R2
O
KOtBu, THF
20 °C, 4 h
1
2
3
4
5
6
7
8
2a
2a
2a
2a
2a
2a
2a
2a
KOtBu (0.375)
KOtBu (0.375)
KOtBu (0.375)
KOtBu (0.375)
KOtBu (0.375)
KOtBu (0.375)
K2CO3 (0.40)
40
4
4
4
4
4
4
4
4
57
57
70
56
50
27
0
R2
H2O2
HCO2H
S
R1
Ar
Ar2I+Cl–
+
R1
S
R1
R2
30
SAr
O
20
Scheme 1 Synthesis of 1-alkenyl aryl sulfides
0
0 to 30
present a new and convenient preparation of 1-alkenyl aryl
sulfides from readily available thiiranes and diaryliodonium
salts in the presence of potassium tert-butoxide (KOtBu) at
room temperature (Scheme 1).
0 (2 h) + 40 (2 h)
20
20
Na2CO3·2 H2O
(0.40)
0
The reaction of phenylthiirane (1a) and diphenyliodoni-
um chloride (2a) on a 0.25-mmol scale was employed as a
model reaction to optimize the reaction conditions (Table
1). Initially, a mixture of 1a and 2a in tetrahydrofuran was
stirred in the presence of KOtBu (0.375 mmol) for 4 hours at
40, 30, 20, or 0 °C, which afforded the desired product phe-
nyl styryl sulfide (3a) in 57%, 57%, 70%, and 56% yields, re-
spectively (Table 1, entries 1–4). When the reaction mix-
ture was stirred in an ice–water bath and then allowed to
warm to 30 °C over 4 hours, 3a was formed in 50% yield (Ta-
ble 1, entry 5). When the reaction mixture was first stirred
at 0 °C for 2 hours and then at 40 °C for another 2 hours, the
yield dropped to 27% (Table 1, entry 6). These results reveal
9
10
11
12
13
14
2a
2a
2a
2a
NaOtBu (0.375)
KOtBu (0.375)
KOtBu (0.40)
KOtBu (0.425)
20
20
20
20
20
20
4
6
4
4
4
4
68
59
71
68
61
60
Ph2I+BF4–(2b) KOtBu (0.40)
Ph2I+PF6– (2c) KOtBu (0.40)
a Reaction conditions: solution of 1a (0.25 mmol) and 2a (0.25 mmol) in THF
(3 mL) stirred in the presence of a base at the indicated temperature and
time.
b Yield on the basis of 1H NMR analysis of the reaction mixture, with 1,3,5-
trimethoxybenzene as an internal standard.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

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J. Dong, J. Xu
Paper
Synthesis
With the optimized reaction conditions in hand, the re-
action scope was then evaluated (Table 2). Various thiiranes
1 were subjected to the optimal reaction conditions.
Phenylthiirane (1a) and electron-rich para/meta/ortho-
methylphenylthiiranes 1b–d gave the corresponding sulfide
products 3b–d in satisfactory to good yields (Table 2, en-
tries 1–4). More electron-rich 2-(4-methoxyphe-
nyl)thiirane (1e) and electron-deficient 4-chloro/bro-
mo/trifluoromethylphenylthiiranes 1f–h produced the de-
sired products 3e–h in satisfactory yields (Table 2, entries
5–8). Cyclohexene sulfide (1i) generated 1-cyclohexen-1-yl
phenyl sulfide (3i) in the highest yield of 82% (Table 2, entry
9). Aliphatic substituted substrate butylthiirane (1j) gave
the desired product 1-hexen-1-yl phenyl sulfide (3j) in 75%
yield (Table 2, entry 10). However, thiirane (1k) itself pro-
duced the corresponding product phenyl vinyl sulfide (3k)
in a low 57% yield (Table 2, entry 11). Sulfides 3 were diffi-
cult to separate from thiiranes and purify, due to the very
close polarities. For accuracy, we have reported the NMR
yields of sulfides 3 (Table 2). For convenient separation and
purification, all obtained sulfides 3 were further oxidized
with performic acid (H2O2/HCO2H) as oxidant to the corre-
sponding sulfones 4 in good yields (Table 2 shows isolated
overall yields from thiiranes 1). With the current method,
only trace amounts (<3%) of cis-1-alkenyl aryl sulfides were
observed on 1H NMR analysis of the reaction mixture in
each case, indicating high stereoselectivity. The cis-isomers
display a larger coupling constant between their two vicinal
alkenic hydrogens than the corresponding trans-isomers.
After oxidation, all obtained sulfones 4 were in the trans-
configuration, assigned by comparison with previously re-
ported data.28–34
Table 2 Substrate Scopea
R2
R2
KOtBu, THF
20 °C, 4 h
S
H2O2
R1
Ar
Ph2I+Cl–
R1
+
S
SAr HCO2H
R2
R1
O
O
2a
1
3
4
Entry
1
1
3
4
S
S
O
S
O
3a 71%
1a
4a 69%
S
S
O
S
2
3
4
5
6
O
3b 75%
1b
4b 56%
S
S
O
S
O
3c 70%
1c
4c 57%
S
S
O
S
O
3d 61%
1d
4d 36%
S
S
O
S
O
O
O
3e 55%
1e
O
4e 55%
S
S
O
S
Cl
O
3f 50%
1f
Cl
Cl
4f 39%
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

D
J. Dong, J. Xu
Paper
Synthesis
Table 2 (continued)
Entry
1
3
4
S
S
O
S
7
8
Br
O
Br
3g 69%
1g
4g 42%
Br
S
S
O
S
F3C
O
F3C
3h 50%
4h 44%
F3C
1h
S
O
S
S
9
10
11
O
1i
3i 82%
4i 57%
O
S
S
O
S
1j
3j 75%
4j 59%
S
O
S
S
O
1k
3k 57%
4k 55%
a Reaction conditions: 1 (0.25 mmol) and 2a (0.25 mmol) were added in THF (3 mL) into a 10-mL reaction vessel; then, KOtBu (0.40 mmol) was added and the
mixture stirred at 20 °C for 4 h. All obtained sulfides 3 were further oxidized to the corresponding sulfones 4 in good yields with H2O2/HCO2H as oxidant. Yields of
sulfones 4 are isolated overall yields from thiiranes 1. All yields of sulfides 3 were determined on the basis of 1H NMR analysis of the reaction mixture, with 1,3,5-
trimethoxybenzene as an internal standard.
Symmetrically substituted bis(4-bromophenyl)iodoni-
um tetrafluoroborate (2d) was treated with thiirane (1k),
followed by oxidation with performic acid for convenient
separation and purification of products, which afforded two
regioisomeric products 4-bromophenyl vinyl sulfone (4ma)
and 3-bromophenyl vinyl sulfone (4mb) in 45% and 22%
yield, respectively, due to thiirane nucleophilic attack at the
different carbon atoms of the 4-bromobenzyne intermedi-
ate generated from 2d (Scheme 2).
Unsymmetrical diaryliodonium salts were also investi-
gated. The reaction of (4-bromophenyl)(phenyl)iodonium
tetrafluoroborate (2e) and thiirane (1k), followed by oxida-
tion, gave not only the regioisomeric products 4-bromo-
phenyl vinyl sulfone (4ma) and 3-bromophenyl vinyl sul-
fone (4mb) in 27% and 17% yield, respectively, but also phe-
nyl vinyl sulfone (4k) in 2% yield (Scheme 2). However, the
reaction of (4-methylphenyl)(phenyl)iodonium tetrafluo-
roborate (2f) and thiirane (1k), followed by oxidation, gen-
erated the regioisomeric products 4-methylphenyl vinyl
sulfone (4na) and 3-methylphenyl vinyl sulfone (4nb) in
13% and 11% yield, respectively, along with phenyl vinyl sul-
fone (4k) in 48% yield (Scheme 2). These results indicate
that the more electron-deficient aryl groups in unsymmet-
ric diaryliodonium salts favor formation of the correspond-
ing benzynes in the presence of base because of their more
acidic hydrogen atoms. 2-Naphthyl(phenyl)iodonium tetra-
fluoroborate (2g) reacted with thiirane (1k), followed by
oxidation, to give rise to the regioisomeric products 1-
naphthyl vinyl sulfone (4oa) and 2-naphthyl vinyl sulfone
(4ob), and phenyl vinyl sulfone (4k) in 19%, 20%, and 34%
yield, respectively, with 10% of 2-(1-naphthyl)thiirane 1,1-
dioxide (5o). Product 5o was generated from the corre-
sponding intermediate 1-(thiiran-1-ium-1-yl)naphthalen-
2-ide (Ao), formed from aryne and thiirane (1k), through
Stevens rearrangement followed by performic acid oxida-
tion (Scheme 2).
Considering the reaction mechanism, the reaction of
phenylthiirane (1a) and diphenyliodonium salts 2 is select-
ed as an example to illustrate the proposed mechanism
(Scheme 3). First, tert-butoxide abstracts a proton from the
ortho-position of diphenyliodonium salt 2 which is fol-
lowed by loss of iodobenzene to afford benzyne. Nucleo-
philic attack of benzyne by triirane 1a generates ylide inter-
mediate A. The phenyl anion intramolecularly abstracts a
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

E
J. Dong, J. Xu
Paper
Synthesis
O
O
O
O
I+
KOtBu, THF
20 °C, 4 h
S
S
H2O2
S
+
–
BF4
+
HCO2H
Br
Br
Br
1k
Br
2d
Br
4ma 45%
4mb 22%
O
O
S
O
O
I+
KOtBu, THF
20 °C, 4 h
O
S
O
H2O2
S
–
+
BF4
+
+
S
Ph
HCO2H
1k
Br
2e
4k 2%
Br
4ma 27%
4mb 17%
O
O
O
O
I+
KOtBu, THF
20 °C, 4 h
S
O
O
S
H2O2
S
–
+
BF4
+
+
S
Ph
HCO2H
1k
2f
4k 48%
4na 13%
4nb 11%
O
S
O
O
O
I+
O
O
O
S
O
KOtBu, THF
20 °C, 4 h
H2O2
S
S
+
–
+
S
+
BF4
+
Ph
4k 34%
HCO2H
1k
2g
4ob 20%
5o 10%
4oa 19%
S
Stevens
rearrangement
S
S+
KOtBu, THF
20 °C, 4 h
H2O2
1k
5o
2g
HCO2H
Ao
2o
Scheme 2 Reactions of thiirane (1k) and symmetrically and unsymmetrically substituted diaryliodonium salts in the presence of potassium tert-butoxide
X
thiiranium intermediates. The sulfides were further oxi-
I
dized with performic acid to the corresponding sulfones.
The current method provides a convenient route for the
(X = Cl, BF4, PF6)
2
preparation of 1-alkenyl aryl sulfides and their sulfones un-
der mild conditions.
KOtBu
S
H
S
S+
+
H
H
H
Unless otherwise noted, all materials were purchased from commer-
cial suppliers. Flash column chromatography was performed using
silica gel (normal phase, 200–300 mesh) from Branch of Qingdao Hai-
yang Chemical Industry. Petroleum ether (PE) used for column chro-
matography was the 30–60 °C fraction, and the removal of residual
solvent was accomplished with a rotary evaporator. Reactions were
monitored by TLC on silica gel GF254 coated 0.2 mm plates from Insti-
tute of Yantai Chemical Industry. The plates were visualized under UV
light, as well as with TLC stains (10% phosphomolybdic acid in EtOH;
3a
H
1a
A
Scheme 3 Proposed mechanism for the synthesis of trans-1-alkenyl
aryl sulfides from thiiranes and diaryliodonium salts in the presence of
potassium tert-butoxide
1% KMnO4 in H2O; 10 g of I2 absorbed on 30 g of silica gel). 1H and 13
C
cis-proton from the thiiranium ring, which is followed by
formation of the C=C bond and ring opening of the thiirani-
um ring, affording the desired trans-product 3a (Scheme 3).
In summary, we have developed a safe and metal-free
method for the synthesis of 1-alkenyl aryl sulfides from
thiiranes and diaryliodonium salts with potassium tert-bu-
toxide as an efficient base. The proposed reaction mecha-
nism involves generation of benzynes from the diaryliodo-
nium salts in the presence of potassium tert-butoxide.
Nucleophilic attack of the benzynes by thiiranes is followed
by hydrogen abstraction and ring opening of the generated
NMR spectra were recorded in CDCl3 on a Bruker 400 MHz spectrom-
eter, with TMS as an internal standard; chemical shifts (δ) are report-
ed in parts per million (ppm). All coupling constants (J) in 1H NMR
spectra are absolute values given in hertz (Hz) with peaks labeled as
singlet (s), broad singlet (br s), doublet (d), triplet (t), quartet (q), and
multiplet (m). Melting points were obtained on a Yanaco MP-500
melting point apparatus and are uncorrected. Diaryliodonium salts 2
were prepared according to the procedure reported by Olofsson and
co-workers.27 The thiiranes 1 and diaryliodonium salts 2 are known
compounds and have analytical data identical to the reported val-
ues.22,27
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

F
J. Dong, J. Xu
Paper
Synthesis
Thiiranes 1; General Procedure22
1H NMR (400 MHz, CDCl3): δ = 8.06 (d, J = 8.0 Hz, 2 H), 7.14 (d, J = 8.0
Hz, 2 H), 3.83 (dd, J = 6.1, 6.1 Hz, 1 H), 2.87 (d, J = 6.5 Hz, 1 H), 2.59 (d,
J = 5.5 Hz, 1 H).
A solution of an oxirane (24.0 mmol) and KSCN (9.31 g, 96.0 mmol) in
H2O (30.0 mL) was stirred at 40 °C for 24 h. The resulting mixture was
diluted with EtOAc and washed with brine. The organic phase was
dried over Na2SO4 and concentrated in vacuo. The residue was puri-
fied by column chromatography (silica gel, PE) to give the correspond-
ing thiirane 1.
13C NMR (101 MHz, CDCl3): δ = 138.2, 131.6, 128.4, 121.3, 35.4, 27.4.
2-[4-(Trifluoromethyl)phenyl]thiirane (1h)22
Colorless oil; yield: 511 mg (42%).
1H NMR (400 MHz, CDCl3): δ = 7.55 (d, J = 8.0 Hz, 2 H), 7.38 (d, J = 8.0
Hz, 2 H), 3.90 (t, J = 5.8 Hz, 1 H), 2.92 (d, J = 6.2 Hz, 1 H), 2.64 (d, J = 5.1
Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ = 143.4, 129.7 (q, JF–C = 32.4 Hz, 1 C),
127.1, 125.5 (q, JF–C = 3.8 Hz, 1 C), 124.0 (q, JF–C = 271.9 Hz, 1 C), 35.0,
27.6.
2-Phenylthiirane (1a)22
Colorless oil; yield: 900 mg (23%).
1H NMR (400 MHz, CDCl3): δ = 7.32–7.21 (m, 5 H), 3.88 (dd, J = 6.5, 5.6
Hz, 1 H), 2.85 (dd, J = 6.6, 1.5 Hz, 1 H), 2.64 (dd, J = 5.7, 1.5 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ = 139.1, 128.5, 127.6, 126.7, 36.1, 27.3.
2-(4-Methylphenyl)thiirane (1b)22
7-Thiabicyclo[4.1.0]heptane (1i)22
Colorless oil; yield: 400 mg (45%).
Colorless oil; yield: 450 mg (20%).
1H NMR (400 MHz, CDCl3): δ = 7.17 (d, J = 7.8 Hz, 2 H), 7.11 (d, J = 7.9
Hz, 2 H), 3.88 (dd, J = 6.3, 6.3 Hz, 1 H), 2.85 (d, J = 6.1 Hz, 1 H), 2.65 (d,
J = 5.1 Hz, 1 H), 2.33 (s, 3 H).
1H NMR (400 MHz, CDCl3): δ = 3.29–3.23 (m, 2 H), 2.22–2.10 (m, 4 H),
1.60–1.51 (m, 2 H), 1.32–1.22 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 37.0, 25.8, 19.4.
13C NMR (101 MHz, CDCl3): δ = 137.4, 136.0, 129.2, 126.6, 36.2, 27.2,
21.1.
2-Butylthiirane (1j)22
Colorless oil; yield: 450 mg (20%).
2-(3-Methylphenyl)thiirane (1c)22
1H NMR (400 MHz, CDCl3): δ = 2.88 (dddd, J = 7.1, 5.8, 5.8, 5.8 Hz, 1 H),
2.50 (dd, J = 6.3, 1.0 Hz, 1 H), 2.15 (dd, J = 5.7, 1.0 Hz, 1 H), 1.85–1.78
(m, 1 H), 1.52–1.34 (m, 5 H), 0.92 (t, J = 7.2 Hz, 3 H).
Colorless oil; yield: 220 mg (25%).
1H NMR (400 MHz, CDCl3): δ = 7.23 (t, J = 7.8 Hz, 1 H), 7.12–7.09 (m, 3
H), 3.90 (dd, J = 6.2, 6.2 Hz, 1 H), 2.89 (d, J = 6.5 Hz, 1 H), 2.69 (d, J = 5.6
Hz, 1 H), 2.37 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 36.3, 36.0, 31.5, 25.9, 22.3, 14.0.
13C NMR (101 MHz, CDCl3): δ = 139.0, 138.3, 128.4, 128.4, 127.2,
123.9, 36.2, 27.3, 21.3.
Phenyl Vinyl Sulfones 4; General Procedure
To a stirring solution of a thiirane 1 (0.25 mmol) and a diaryliodoni-
um salt 2 (0.25 mmol) in anhydrous THF (3 mL) open to air at 20 °C
was added KOtBu (45 mg, 0.40 mmol). The resulting mixture was
stirred at 20 °C for 4 h. After removal of the solvent, H2O was added.
The solution was extracted with CH2Cl2 and the combined organic ex-
tracts were concentrated to afford the crude product sulfide 3, which
was used directly in the next step without purification.
2-(2-Methylphenyl)thiirane (1d)22
Colorless oil; yield: 147 mg (10%).
1H NMR (400 MHz, CDCl3): δ = 7.19–7.15 (m, 4 H), 4.01 (dd, J = 6.4, 6.4
Hz, 1 H), 2.87 (d, J = 6.5 Hz, 1 H), 2.74 (d, J = 5.9 Hz, 1 H), 2.49 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 137.8, 136.9, 130.0, 127.5, 126.2,
For the reactions of thiirane (1k) with diaryliodonium salts 2d–g, a
solution of 1k (45 mg, 0.75 mmol) and salt 2 (0.25 mmol) in THF (3
mL) was stirred in the presence of KOtBu (45 mg, 0.40 mmol) at 20 °C
for 4 h.
125.4, 34.4, 25.6, 19.5.
2-(4-Methoxyphenyl)thiirane (1e)22
Colorless oil; yield: 107 mg (17%).
To a performic acid solution, prepared by mixing and stirring 30%
H2O2 (0.17 mL, 1.5 mmol) and 88% HCO2H (1.5 mL) at r.t. for 0.5 h in
an ice bath, was added dropwise the crude sulfide 3 obtained from
the above step at 0 °C over a period of 10 min. The resulting mixture
was stirred and allowed to warm to r.t. for 0.5–1 h. The resulting mix-
ture was washed with H2O. The organic phase was dried over anhy-
drous Na2SO4 and concentrated in vacuo. The residue was purified by
column chromatography to give the sulfone 4 in moderate to good
yields.22 All of the sulfones are known compounds and have analytical
data identical to the reported values.28–34
1H NMR (400 MHz, CDCl3): δ = 7.20 (d, J = 8.2 Hz, 2 H), 6.84 (d, J = 8.3
Hz, 2 H), 3.89 (dd, J = 6.3, 6.3 Hz, 1 H), 3.80 (s, 3 H), 2.84 (d, J = 6.5 Hz,
1 H), 2.63 (d, J = 5.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ = 159.1, 130.9, 127.8, 114.0, 55.3, 36.2,
27.1.
2-(4-Chlorophenyl)thiirane (1f)22
Colorless oil; yield: 431 mg (43%).
1H NMR (400 MHz, CDCl3): δ = 7.26 (d, J = 8.1 Hz, 2 H), 7.20 (d, J = 8.2
Hz, 2 H), 3.84 (dd, J = 6.1, 6.1 Hz, 1 H), 2.86 (d, J = 6.5 Hz, 1 H), 2.59 (d,
J = 5.5 Hz, 1 H).
[(E)-2-(Phenylsulfonyl)vinyl]benzene (4a)28
White solid; yield: 42 mg (69%); mp 80–81 °C; Rf = 0.18 (hexanes–
EtOAc, 10:1).
13C NMR (101 MHz, CDCl3): δ = 137.7, 133.2, 128.7, 128.0, 35.3, 27.4.
1H NMR (400 MHz, CDCl3): δ = 7.96 (d, J = 7.4 Hz, 2 H), 7.69 (d, J = 15.2
Hz, 1 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.55 (t, J = 8.1 Hz, 2 H), 7.50–7.47 (m,
2 H), 7.41–7.39 (m, 3 H), 6.87 (d, J = 15.4 Hz, 1 H).
2-(4-Bromophenyl)thiirane (1g)22
Colorless oil; yield: 407 mg (32%).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

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J. Dong, J. Xu
Paper
Synthesis
13C NMR (101 MHz, CDCl3): δ = 142.4, 140.7, 133.3, 132.3, 131.2,
1-[(E)-2-(Phenylsulfonyl)vinyl]-4-(trifluoromethyl)benzene (4h)30
129.3, 129.0, 128.5, 127.6, 127.2.
White solid; yield: 34 mg (44%); mp 145–146 °C; Rf = 0.20 (hexanes–
EtOAc, 10:1).
1-Methyl-4-[(E)-2-(phenylsulfonyl)vinyl]benzene (4b)29
1H NMR (400 MHz, CDCl3): δ = 7.96 (d, J = 7.60 Hz, 2 H), 7.71 (d, J =
15.7 Hz, 1 H), 7.66–7.64 (m, 3 H), 7.61–7.55 (m, 4 H), 6.96 (d, J = 15.3
Hz, 1 H).
White solid; yield: 36 mg (56%); mp 139–140 °C; Rf = 0.33 (hexanes–
EtOAc, 10:1).
1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.2 Hz, 2 H), 7.66 (d, J = 15.5
Hz, 1 H), 7.61–7.59 (m, 1 H), 7.54 (t, J = 7.7 Hz, 2 H), 7.38 (d, J = 8.2 Hz,
2 H), 7.19 (d, J = 8.2 Hz, 2 H), 6.81 (d, J = 15.3 Hz, 1 H), 2.37 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 140.4, 140.1, 135.7, 133.7, 132.6 (q,
JF–C = 32.8 Hz, 1 C), 130.0, 129.4, 128.7, 127.8, 126.0 (q, JF–C= 3.8 Hz, 1
C), 123.6 (q, JF–C = 272.3 Hz, 1 C).
13C NMR (101 MHz, CDCl3): δ = 142.5, 141.8, 140.9, 133.2, 129.8,
129.6, 129.2, 128.5, 127.5, 126.0, 21.5.
(1-Cyclohexen-1-ylsulfonyl)benzene (4i)31
Colorless liquid; yield: 31 mg (57%); Rf = 0.21 (hexanes–EtOAc, 10:1).
1-Methyl-3-[(E)-2-(phenylsulfonyl)vinyl]benzene (4c)28
1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 7.5 Hz, 2 H), 7.59 (t, J = 7.5
Hz, 1 H), 7.51 (t, J = 7.5 Hz, 2 H), 7.05 (s, 1 H), 2.27–2.23 (m, 2 H),
2.17–2.13 (m, 2 H), 1.65–1.52 (m, 4 H).
White solid; yield: 37 mg (57%); mp 75–77 °C; Rf = 0.26 (hexanes–
EtOAc, 10:1).
1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.3 Hz, 2 H), 7.66 (d, J = 15.5
Hz, 1 H), 7.62 (t, J = 7.0 Hz, 1 H), 7.54 (t, J = 7.0 Hz, 2 H), 7.30–7.21 (m,
4 H), 6.85 (d, J = 15.4 Hz, 1 H), 2.35 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 139.7, 139.4, 138.4, 133.0, 129.0,
127.9, 25.4, 22.8, 21.7, 20.7.
13C NMR (101 MHz, CDCl3): δ = 142.7, 140.8, 138.8, 133.3, 132.2,
[(E)-1-Hexen-1-ylsulfonyl]benzene (4j)32
132.0, 129.3, 129.2, 129.1, 128.9, 127.6, 127.0, 125.8, 21.2.
Colorless liquid; yield: 33 mg (59%); Rf = 0.34 (hexanes–EtOAc, 10:1).
1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J = 7.9 Hz, 2 H), 7.60 (t, J = 7.2
Hz, 1 H), 7.53 (t, J = 7.6 Hz, 2 H), 6.99 (dt, J = 6.7, 14.6 Hz, 1 H), 6.30 (d,
J = 14.9 Hz, 1 H), 2.23 (dt, J = 7.1, 7.1 Hz, 2 H), 1.44 (quin, J = 7.1 Hz, 2
H), 1.33 (tq, J = 7.1, 7.1 Hz, 2 H), 0.88 (t, J = 7.3 Hz, 3 H).
1-Methyl-2-[(E)-2-(phenylsulfonyl)vinyl]benzene (4d)28
White solid; yield: 24 mg (36%); mp 74–75 °C; Rf = 0.26 (hexanes–
EtOAc, 10:1).
1H NMR (400 MHz, CDCl3): δ = 7.99–7.95 (m, 3 H), 7.63 (t, J = 7.0 Hz, 1
H), 7.56 (t, J = 7.5 Hz, 2 H), 7.44 (d, J = 7.8 Hz, 1 H), 7.30 (t, J = 7.5 Hz, 1
H), 7.23–7.17 (m, 2 H), 6.79 (d, J = 15.4 Hz, 1 H), 2.46 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 147.3, 140.7, 133.1, 130.3, 129.2,
129.1, 127.5, 31.1, 29.6, 22.1, 13.7.
13C NMR (101 MHz, CDCl3): δ = 140.7, 140.1, 138.2, 133.3, 131.3,
(Vinylsulfonyl)benzene (4k)33
131.0, 130.9, 129.3, 128.2, 127.7, 126.9, 126.5, 19.8.
White solid; yield: 23 mg (55%); mp 69–70 °C; Rf = 0.17 (hexanes–
EtOAc, 10:1).
1-Methoxy-4-[(E)-2-(phenylsulfonyl)vinyl]benzene (4e)29
1H NMR (400 MHz, CDCl3): δ = 7.89 (d, J = 7.8 Hz, 2 H), 7.63 (t, J = 7.1
Hz, 1 H), 7.54 (t, J = 7.8 Hz, 2 H), 6.66 (dd, J = 9.6, 16.5 Hz, 1 H), 6.45 (d,
J = 16.6 Hz, 1 H), 6.03 (d, J = 9.7 Hz, 1 H).
White solid; yield: 36 mg (55%); mp 73–74 °C; Rf = 0.18 (hexanes–
EtOAc, 10:1).
1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 7.84 Hz, 2 H), 7.63 (d, J =
15.3 Hz, 1 H), 7.60 (t, J = 7.3 Hz, 1 H), 7.53 (t, J = 8.0 Hz, 2 H), 7.43 (d,
J = 8.4 Hz, 2 H), 6.89 (d, J = 8.4 Hz, 2 H), 6.71 (d, J = 15.3 Hz, 1 H), 3.82
(s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 139.5, 138.4, 133.6, 129.3, 127.9,
127.7.
Mixture of 1-Bromo-4-(vinylsulfonyl)benzene (4ma) and 1-Bro-
mo-3-(vinylsulfonyl)benzene (4mb)33
13C NMR (101 MHz, CDCl3): δ = 162.0, 142.2, 141.1, 133.1, 130.3,
129.2, 127.4, 124.9, 124.4, 114.5, 55.4.
Colorless liquid; yield: 43 mg (4ma: 45%, 4mb: 22%).
1H NMR (400 MHz, CDCl3): δ (4ma) = 7.75 (d, J = 8.7 Hz, 2 H), 7.69 (d,
J = 8.7 Hz, 2 H), 6.68–6.61 (m, 1 H), 6.47 (d, J = 11.1 Hz, 1 H), 6.07 (d,
J = 9.9 Hz, 1 H).
1H NMR (400 MHz, CDCl3): δ (4mb) = 8.03 (s, 1 H), 7.83 (d, J = 7.0 Hz,
1 H), 7.76–7.74 (m, 1 H), 7.43 (t, J = 7.9 Hz, 1 H), 6.68–6.61 (m, 1 H),
6.50 (d, J = 16.5 Hz, 1 H), 6.10 (d, J = 9.9 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ (4ma + 4mb) = 141.5, 139.0, 138.6,
138.1, 137.9, 136.7, 133.4, 132.6, 130.9, 130.8, 129.4, 129.0, 128.8,
128.4, 126.4, 123.2.
1-Chloro-4-[(E)-2-(phenylsulfonyl)vinyl]benzene (4f)28
White solid; yield: 27 mg (39%); mp 139–140 °C; Rf = 0.58 (hexanes–
EtOAc, 3:1).
1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.6 Hz, 2 H), 7.65–7.61 (m, 2
H), 7.55 (t, J = 7.8 Hz, 2 H), 7.41 (d, J = 8.6 Hz, 2 H), 7.36 (d, J = 8.6 Hz, 2
H), 6.84 (d, J = 15.5 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ = 140.9, 140.4, 137.2, 133.5, 130.8,
129.7, 129.4, 127.9, 127.7.
1-Bromo-4-[(E)-2-(phenylsulfonyl)vinyl]benzene (4g)29
Mixture of 1-Bromo-4-(vinylsulfonyl)benzene (4ma), 1-Bromo-3-
(vinylsulfonyl)benzene (4mb), and (Vinylsulfonyl)benzene (4k)33
White solid; yield: 34 mg (42%); mp 168–169 °C; Rf = 0.29 (hexanes–
EtOAc, 10:1).
White solid; yield: 27 mg (4ma: 27%, 4mb: 17%, 4k: 2%).
1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 7.6 Hz, 2 H), 7.65–7.51 (m, 6
H), 7.34 (d, J = 8.2 Hz, 2 H), 6.86 (d, J = 15.4 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ = 141.0, 140.4, 133.5, 132.3, 131.2,
1H NMR (400 MHz, CDCl3): δ (4ma) = 7.75 (d, J = 8.7 Hz, 2 H), 7.69 (d,
J = 8.7 Hz, 2 H), 6.68–6.61 (m, 1 H), 6.47 (d, J = 11.1 Hz, 1 H), 6.07 (d,
J = 9.9 Hz, 1 H).
129.9, 129.4, 128.0, 127.7, 125.6.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

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J. Dong, J. Xu
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Synthesis
1H NMR (400 MHz, CDCl3): δ (4mb) = 8.03 (s, 1 H), 7.83 (d, J = 7.0 Hz,
1 H), 7.76–7.74 (m, 1 H), 7.43 (t, J = 7.9 Hz, 1 H), 6.68–6.61 (m, 1 H),
6.50 (d, J = 16.5 Hz, 1 H), 6.10 (d, J = 9.9 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ (4ma + 4mb + 4k) = 141.5, 139.0, 138.6,
138.1, 137.9, 136.7, 133.4, 132.6, 130.9, 130.8, 129.4, 129.0, 128.8,
128.4, 126.4, 123.2.
References
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Tetrahedron 2008, 64, 10670.
Mixture of 1-Methyl-4-(vinylsulfonyl)benzene (4na), 1-Methyl-3-
(vinylsulfonyl)benzene (4nb), and (Vinylsulfonyl)benzene (4k)33
White solid; yield: 31 mg (4na: 13%, 4nb: 11%, 4k: 48%).
1H NMR (400 MHz, CDCl3): δ (4na) = 7.76 (d, J = 8.0 Hz, 2 H), 7.33 (d,
J = 8.0 Hz, 2 H), 6.69–6.60 (m, 1 H), 6.47–6.39 (m, 1 H), 6.05–5.98 (m,
1 H), 2.43–2.42 (m, 3H).
1H NMR (400 MHz, CDCl3): δ (4nb) = 7.69–7.61 (m, 2 H), 7.43–7.42
(m, 2 H), 6.69–6.60 (m, 1 H), 6.47–6.39 (m, 1 H), 6.05–5.98 (m, 1 H),
2.43–2.42 (m, 3H).
13C NMR (101 MHz, CDCl3): δ (4na + 4nb + 4k) = 144.7, 139.6, 139.5,
138.7, 138.5, 138.4, 136.5, 134.4, 133.6, 129.9, 129.3, 129.2, 128.1,
127.9, 127.8, 127.7, 127.5, 127.1, 125.0, 21.6, 21.3.
Mixture of 1-(Vinylsulfonyl)naphthalene (4oa) and 2-(Naphtha-
len-1-yl)thiirane 1,1-Dioxide (5o)19
White solid; yield: 15 mg (4oa: 19%, 5o: 10%).
1H NMR (400 MHz, CDCl3): δ (4oa) = 8.62 (d, J = 8.6 Hz, 1 H), 8.37 (dd,
J = 7.3, 1.2 Hz, 1 H), 8.13 (d, J = 7.4 Hz, 1 H), 7.99–7.94 (m, 1 H), 7.72–
7.66 (m, 1 H), 7.64–7.59 (m, 2 H), 6.79 (dd, J = 16.5, 9.8 Hz, 1 H), 6.58
(d, J = 16.5 Hz, 1 H), 6.08 (d, J = 9.8 Hz, 1 H).
1H NMR (400 MHz, CDCl3): δ (5o) = 8.13 (d, J = 7.4 Hz, 1 H), 8.05 (d, J =
8.2 Hz, 1 H), 7.99–7.94 (m, 2 H), 7.72–7.66 (m, 1 H), 7.64–7.59 (m, 2
H), 4.88 (dd, J = 9.7, 5.2 Hz, 1 H), 4.24 (dd, J = 11.9, 9.7 Hz, 1 H), 3.97
(dd, J = 11.9, 5.2 Hz, 1 H).
(11) Singh, R.; Raghuvanshi, D. S.; Singh, K. N. Org. Lett. 2013, 15,
4202.
13C NMR (101 MHz, CDCl3): δ (4oa + 5o) = 138.6, 135.4, 134.3, 134.1,
133.4, 132.3, 130.3, 129.3, 129.2, 128.7, 128.5, 127.9, 127.8, 127.0,
126.9, 125.8, 125.3, 124.6, 124.2, 120.7, 75.2, 42.8.
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637.
Mixture of 2-(Vinylsulfonyl)naphthalene (4ob) and (Vinylsulfo-
nyl)benzene (4k)34
White solid; yield: 25 mg (4ob: 20%, 4k: 34%).
1H NMR (400 MHz, CDCl3): δ (4ob) = 8.50 (d, J = 1.2 Hz, 1 H), 7.99 (d,
J = 8.4 Hz, 2 H), 7.93–7.89 (m, 1 H), 7.82 (dd, J = 8.7, 1.9 Hz, 1 H), 7.69–
7.61 (m, 2 H), 6.72 (dd, J = 16.5, 9.8 Hz, 1 H), 6.51 (d, J = 16.5 Hz, 1 H),
6.06 (d, J = 9.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3): δ (4ob + 4k) = 139.5, 138.5, 138.4, 136.3,
135.2, 133.6, 132.2, 129.7, 129.7, 129.4, 129.3, 128.0, 127.9, 127.8,
127.7, 127.7, 122.6.
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Funding Information
This work was supported by the National Natural Science Foundation
(22) (a) Yu, H.; Cao, S. L.; Zhang, L. L.; Liu, G.; Xu, J. X. Synthesis 2009,
2205. (b) Li, X. Y.; Xu, J. X. Tetrahedron 2011, 67, 1681.
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X. P.; Xu, J. X. Tetrahedron Lett. 2017, 58, 1651. (c) Li, S. Q.; Chen,
X. P.; Xu, J. X. Tetrahedron 2018, 74, 1613.
of China (Nos. 21572017 and 21772010).
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0036-1591559. Copies of the 1H and 13C
NMR spectra of products 4 are included.
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Synthesis
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