PhI(OAc)2/KI mediated 1,2-acetoxysulfenylation of alkenes: Facile synthesis of β-acetoxysulfides

Article abstract of DOI:10.1016/j.tet.2013.08.018

A convenient method for 1,2-acetoxysulfenylation of alkenes using disulfide promoted by (diacetoxyiodo)benzene (PhI(OAc)₂, DIB)/KI was developed. The reaction is highly regioselective for styrene derivatives while aliphatic alkenes lead to a mixture of two regioisomers.

Full text of DOI:10.1016/j.tet.2013.08.018

Accepted Manuscript
PhI(OAc) /KI mediated 1,2-acetoxysulfenylation of alkenes: Facile synthesis of β-
2
acetoxysulfides
Charoensak Muangkaew, Praewpan Katrun, Patcharaphon Kanchanarugee, Manat
Pohmakotr, Vichai Reutrakul, Darunee Soorukram, Thaworn Jaipetch, Chutima
Kuhakarn
PII:
S0040-4020(13)01292-1
10.1016/j.tet.2013.08.018
TET 24707
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 April 2013
Revised Date: 25 July 2013
Accepted Date: 12 August 2013
Please cite this article as: Muangkaew C, Katrun P, Kanchanarugee P, Pohmakotr M, Reutrakul V,
Soorukram D, Jaipetch T, Kuhakarn C, PhI(OAc) /KI mediated 1,2-acetoxysulfenylation of alkenes:
2
Facile synthesis of β-acetoxysulfides, Tetrahedron (2013), doi: 10.1016/j.tet.2013.08.018.
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ACCEPTED MANUSCRIPT
Graphical Abstract
PhI(OAc)2/KI mediated 1,2-acetoxysulfenylation of
Leave this area blank for abstract info.
alkenes: Facile synthesis of β-acetoxysulfides
Charoensak Mueangkaewa, Praewpan Katruna, Patcharaphon Kanchanarugeea, Manat Pohmakotra, Vichai
Reutrakula, Darunee Soorukrama, Thaworn Jaipetchb and Chutima Kuhakarna,
aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of
Science, Mahidol University, bMahidol University, Kanchanaburi Campus, Thailand
OAc
SAr
OAc
PhI(OAc)2
PhI(OAc)2
SAr
OAc
SAr
+
R
R
R
R
ArSSAr, KI
ArSSAr, KI
CH2Cl2, r.t.
minor
R = Alkyl
Ar = Ph, 4-MeC6H4,
4-MeOC6H4, 4-FC6H4
major
ClCH2CH2Cl, reflux
single isomer
R = Aryl
Ar = Ph, 4-MeC6H4,
4-MeOC6H4, 4-FC6H4

ACCEPTED MANUSCRIPT
1
Tetrahedron
journal homepage: www.elsevier.com
PhI(OAc)2/KI mediated 1,2-acetoxysulfenylation of alkenes: Facile synthesis of β-
acetoxysulfides
Charoensak Muangkaewa, Praewpan Katruna, Patcharaphon Kanchanarugeea, Manat Pohmakotra, Vichai
Reutrakula, Darunee Soorukrama, Thaworn Jaipetchb and Chutima Kuhakarna,
aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama VI Road,
Bangkok 10400, Thailand
bMahidol University, Kanchanaburi Campus, Saiyok, Kanchanaburi 71150, Thailand
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A convenient method for 1,2-acetoxysulfenylation of alkenes using disulfide promoted by
(diacetoxyiodo)benzene (PhI(OAc)2, DIB)/KI was developed. The reaction is highly
regioselective for styrene derivatives while aliphatic alkenes lead to a mixture of two
regioisomers.
Available online
2013 Elsevier Ltd. All rights reserved.
Keywords:
PhI(OAc)2
Acetoxysulfenylation
Acetoxysulfides
Oxidation
Sulfides
———
Corresponding author. Tel.: +66 2201 5155; fax: +66 2354 7151. e-mail address: chutima.kon@mahidol.ac.th

ACCEPTED MANUSCRIPT
2
Tetrahedron
1. Introduction
promoted at all (Table 1, entries 13-14). Finally, if diphenyl
disulfide was excluded from the reaction, the crude mixture
contained the corresponding 1-(4-bromophenyl)-2-iodoethyl
acetate and p-bromostyrene was recovered also in a ratio of 1 : 2
(1H NMR analysis) (Table 1, entry 15).
1,2-Hydroxysulfides are important class of compounds. They
are valued as crucial building blocks for the preparation of useful
and higher functionalized organic molecules.1 Additionally, 1,2-
hydroxysulfide-containing molecules have been shown to exhibit
biological activities,2 or exist as important intermediates in
pharmacological fields.3 There are a number of methods available
for preparation of 1,2-hydroxysulfides including, thiolysis of
epoxides,4 reactions of α-chlorosulfides or α-trimethylsilyl
sulfides with carbonyl compounds,5 thiol-oxygen cooxidation
reactions (TOCOs) of olefins,6 reactions between alkenes and
thiols in β-cyclodextrin/H2O/O2,7 or [bmim][BF4]/H2O/O2,8 and
reaction between alkenes and disulfides mediated by Zn/AlCl3
system.9 In contrast to the developed methods for the synthesis of
1,2-hydroxysulfides, those for the synthesis of 1,2-acyloxysulfide
are very limited. To date, the reactions of alkenes and disulfides
mediated by Pb(OAc)4,10 or Cu(OAc)2,11 CuI-bpy,12 and CuI-
imidazole13 have been reported. However, the methods required
toxic metal salts, stoichiometric amount of the disulfides or
lengthy reaction time.
Table 1 Optimization of reaction conditions.a
OAc
SPh
PhI(OAc)2, KI
SPh
SPh
SO2Ph
Ar
PhSSPh
Ar
Ar
Ar
+
solvent, rt, time
+
+
1a
2a
3aa
4aa
5aa
Ar = 4-BrC6H4
PhI(OAc)2
[equiv.]
KI
[equiv.]
Solvents
Time
[h]
Yield [%]b
3aa 4aa 5aa
Entry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.0
2.0
1.2
1.2
-
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
2.0
-
CH3CN
H2O
DMSO
THF
3
3
3
3
3
3
3
3
2
2
2
2
2
2
20
19
3
-
-
-
-
4
-
19
-
-
-
-
-
-
-
32
7
1
1
3
-
-
-
18
-
11
10
81
10
68
82
64
73
58
-
EtOAc
CH2Cl2
CHCl3
ClCH2CH2Cl
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
As a part of our continuing interest in hypervalent iodine
chemistry, we seek novel synthetic applications of o-
iodoxybenzoic acid (IBX) and (diacetoxyiodo)benzene
(PhI(OAc)2, DIB). Recently, we reported a convenient synthesis
-
-
-
1.0
-
-
of vinyl sulfones and β-iodovinyl sulfones from alkenes and
alkynes with arenesulfinate sodium salts mediated by
PhI(OAc)2/KI in CH3CN.14 Having envisioned that oxy-
sulfenylation of alkenes is an important approach for the vicinal
installation of an oxygen moiety (HO-, RO-, or RCO2-) and an
organosulfur to the olefinic moiety, we now report our findings
on 1,2-acetoxysulfenylation of alkenes using disulfide mediated
by (diacetoxyiodo)benzene (PhI(OAc)2) and potassium iodide (KI).
OAc
15c
1.2
1.0
CH2Cl2
2
I
p-BrC6H4
(35%)d
a All reactions were performed using p-bromostyrene (0.5 mmol) and PhSSPh
(0.6 equiv.).
b Isolated yields.
c The reaction was carried out without added PhSSPh.
d % Conversion of 1-(4-bromophenyl)-2-iodoethyl acetate was determined by
1H NMR integration.
2. Results and Discussion
In order to optimize the iodide source, a brief study on the
reactions employing several kinds of iodide sources was studied.
Among the iodide sources screened including LiI, NaI, KI, CuI,
Et4NI, Bu4NI and molecular iodine (I2), potassium iodide (KI)
gave appreciable results while others led to either low yields of
1,2-acetoxysulfide 3aa or unselective formation of products 3aa,
4aa and 5aa. Finally, the type of halide also has an effect on the
reaction; no reaction took place when KBr and NaCl were
employed in place of KI.
The reaction of p-bromostyrene and diphenyl disulfide was
investigated under a variety of reaction conditions in order to
optimize the reaction conditions (Table 1). Based on our previous
report, acetonitrile was first attempted as a solvent for the
reaction.14 The reaction of p-bromostyrene using PhI(OAc)2 (1.2
equiv.), PhSSPh (0.6 equiv.) and KI (1.0 equiv.) in acetonitrile at
room temperature for 3 h gave incomplete reaction and yielded
the corresponding 1,2-acetoxysulfide 3aa in 20% yield as a
single isomer15 (Table 1, entry 1). A similar yield of 3aa was
On the basis of the optimization results described above, the
optimum reaction conditions used a dichloromethane solution of
alkene 1 (1 equiv.) in the presence of PhI(OAc)2 (1.2 equiv.), KI
(1.0 equiv.), disulfide (0.6 equiv.), and the reaction mixture was
stirred at room temperature for 2 h. We next carried out a 1,2-
acetoxysulfenylation of structurally different styrene derivatives
1 using disulfides 2 mediated by PhI(OAc)2/KI and the results are
summarized in Table 2.
1
obtained, albeit with more complex H NMR and TLC patterns,
when water was employed as the solvent (Table 1, entry 2). In
DMSO, the p-bromostyrene was consumed completely but the
desired product 3aa was not detected (1H NMR analysis; Table 1,
entry 3). The use of tetrahydrofuran and ethyl acetate gave a
mixture of products including 3aa, 1,2-dithioether 4aa and vinyl
sulfone 5aa (Table 1, entries 4-5). Gratifyingly, the reaction
proceeded smoothly in dichloromethane affording 1,2-
acetoxysulfide 3aa in 81% yield (Table 1, entry 6). Poorer results
were observed when chloroform and 1,2-dichloroethane were
employed as the solvents (Table 1, entries 7-8). It is worth
mentioning that mixture of compounds and recovered p-
bromostyrene (1H NMR and TLC analyses) were observed when
toluene, acetone and methanol were employed as the solvents. In
particular, reaction carried out in methanol gave competing
methoxy trapping product and methyl benzenesulfinate as major
components. The reaction time can be decreased from 3 h to 2 h
without deteriorating reaction efficiency (Table 1, entries 6 vs 9).
The yields of 3aa slightly dropped when PhI(OAc)2 was
employed in lesser or greater amount than 1.2 equivalents (Table
1, entries 10-11). An excess amount of KI was harmful to the
reaction leading to a mixture of products (Table 1, entry 12). In
the absence of either PhI(OAc)2 or KI, the reaction was not
As shown in Table 2, except for those of p-methoxystyrene
(1h), the reactions between styrene derivatives 1a-m with
diphenyl disulfide (2a) in general afforded the corresponding 1,2-
acetoxysulfides in good yields (63-85% yields) (Table 2, entries
1-13). Furthermore, the use of p-methylphenyl disulfide (2b)
(Table 2, entries 14-20), p-methoxyphenyl disulfide (2c) (Table
2, entries 21-26), and p-fluorophenyl disulfide (2d) (Table 2,
entries 27-33) also gave comparable results. It is worth
mentioning that moderate yield (58% yield) of the 1,2-
acetoxysulfenylation of p-methoxystyrene (1h) was obtained
when electron rich-substituted disulfides 2b was employed
(Table 2, entry 8 vs entry 17) while electron deficient-substituted
disulfides 2d gave poor results (Table 2, entry 30).

ACCEPTED MANUSCRIPT
3
Table 3 PhI(OAc)2/KI mediated 1,2-acetoxysulfenylation of
aliphatic alkenes using disulfides.a
Table 2 PhI(OAc)2/KI mediated 1,2-acetoxysulfenylation of
OAc
SAr
styrene derivatives using disulfides.a
PhI(OAc)2, ArSSAr
SAr
OAc
R
R
R
ClCH2CH2Cl, reflux, 2 h
7
7'
6
Entry
Alkenes
Products;
Ar =
Yield [%]b(7:7')c
66 (7aa:7'aa = 1.9:1)
58 (7ba:7'ba = 1.9:1)
48 (7ca:7'ca = 3.7:1)
65 (7da:7'da = 3.7:1)
67 (7ea:7'ea = 2.4:1)
1
2
3
4
5
6
6a
6b
6c
6d
6e
6f
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
5
Br
3
Entry
Substrate;
Ar1 =
Product;
Ar2 =
Yield
[%]b
O
1
2
3
4
5
6
7
8
p-BrC6H4
C6H5
p-ClC6H4
1a
1b
1c
1d
1e
1f
1g
1h
1i
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
3aa
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
82
85
82
79
71
78
82
33
75
68
63
69
76
85
88
88
58
81
72
84
88
81
86
78
72
84
74
82
80
23
51
59
61
O
p-FC6H4
p-CH3C6H4
p-ClCH2C6H4
p-CH3COOC6H4
p-CH3OC6H4
m-ClC6H4
m-FC6H4
m-OHCC6H4
m-O2NC6H4
o-ClC6H4
p-BrC6H4
p-ClC6H4
p-FC6H4
p-CH3OC6H4
m-ClC6H4
m-OHCC6H4
o-ClC6H4
p-BrC6H4
p-ClC6H4
MeO
MeO
MeO
70 (7fa; single isomer)
9
SC6H5
10
11c
12c
13
14
15
16
17
18
19c
20
21
22
23
24
25c
26
27
28
29
30
31
32c
33
1j
1k
1l
3ja
3ka
3la
OAc
7
8
9
6a
6e
6f
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
71 (7ab:7'ab = 2.4:1)
1m
1a
1c
1d
1h
1i
1k
1m
1a
1c
1d
1i
1k
1m
1a
1c
1d
1h
1i
3ma
3ab
3cb
3db
3hb
3ib
3kb
3mb
3ac
3cc
3dc
3ic
3kc
3mc
3ad
3cd
3dd
3hd
3id
5
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
p-CH3OC6H4
p-CH3OC6H4
p-CH3OC6H4
p-CH3OC6H4
p-CH3OC6H4
p-CH3OC6H4
p-FC6H4
p-FC6H4
p-FC6H4
p-FC6H4
p-FC6H4
p-FC6H4
p-FC6H4
80 (7eb:7'eb = 2.2:1)
56 (7fb; single isomer)
S(p-CH3C6H4)
OAc
10
11
12
6a
6e
6f
p-CH3OC6H4
p-CH3OC6H4
p-CH3OC6H4
73 (7ac:7'ac = 2.0:1)
p-FC6H4
5
m-ClC6H4
m-OHCC6H4
o-ClC6H4
p-BrC6H4
p-ClC6H4
62 (7ec:7'ec = 3.4:1)
73 (7fc; single isomer)
p-FC6H4
S(p-CH3OC6H4)
p-CH3OC6H4
m-ClC6H4
m-OHCC6H4
o-ClC6H4
OAc
1k
1m
3kd
3md
13
14
15
6a
6e
6f
p-FC6H4
p-FC6H4
p-FC6H4
74 (7ad:7'ad = 1.8:1)
5
a
All reactions were performed using substrate (0.5 mmol), PhI(OAc)2
(1.2 equiv.), KI (1 equiv.) and disulfide (0.6 equiv.) in CH2Cl2 at room
temperature for 2 h.
70 (7ed:7'ed = 2.3:1)
MeO
b Isolated yields.
c The reaction was allowed to stir overnight.
69 (7fd; single isomer)
S(p-FC6H4)
Having accomplished the 1,2-acetoxysulfenylation of styrene
derivatives, we next carried out the 1,2-acetoxysulfenylation of
simple alkenes as summarized in Table 3. Under standard
reaction conditions used for styrene derivatives, the reaction of 1-
octene (6a) and diphenyl disulfide (2a) did not give the
corresponding product while the starting 1-octene (6a) was
totally consumed. To our delight, we found that the reaction of 1-
octene (6a) and diphenyl disulfide (2a) proceeded in refluxing
1,2-dichloroethane, affording a 1.9:1 ratio of two isomeric 1,2-
acetoxysulfides 7aa and 7'aa in 66% yield (Table 3, entry 1).16
Unfortunately, the mixture was inseparable by chromatography.
Terminal aliphatic alkenes including those containing bromine
atom, oxygen atom gave the corresponding products in moderate
to good yields albeit as a mixture of two regioisomers (Table 3).
Cyclohexene, a symmetrical alkene, gave the corresponding 1,2-
acetoxysulfenylation product in good yields as a single isomer
(trans) (Table 3, entries 6, 9, 12, 15).12
OAc
a All reactions were performed using substrate (0.5 mmol), PhI(OAc)2 (1.2
equiv.), KI (1 equiv.) and disulfide (0.6 equiv.) in refluxing ClCH2CH2Cl for
2 h.
b Isolated yields.
Ratios were determined by 1H-NMR integration of a methine proton of
c
PhSCH (major isomer) and that of AcOCH (B).
From the experimental results described, a probable reaction
mechanism is suggested (Scheme 1). It has been previously
reported that PhI(OAc)2 reacts with iodide anion, yielding
acetylhypoiodite (AcOI, A) as a putative intermediate.17 The
AcOI formed can react with double bond of the alkene substrate
if the diaryl disulfide is not present leading to iodoacetoxy
compound (Table 1, entry 15). However, this conversion is rather
1
slow (35% conversion after 2 h by H NMR analysis). Thus, in
the presence of the added diaryl disulfide reagent (ArSSAr), we
believed that the acetylhypoiodite (AcOI, A) readily reacts with

ACCEPTED MANUSCRIPT
4
Tetrahedron
diaryl disulfide substrate to furnish electrophilic thionium
DIB (0.6 mmol, 193 mg), ArSSAr (0.3 mmol) and KI (0.5
mmol, 83 mg) were added to a styrene (or their derivatives)
solution in CH2Cl2 (0.5 mmol in 2 mL of CH2Cl2), and the
suspension mixture was vigorously stirred at room temperature
for 2 h. Upon completion, 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), brine (20 mL), dried
(anhydrous MgSO4), filtered, and concentrated (aspirator). The
residue was purified by column chromatography (SiO2) to furnish
analytically pure product.
intermediate B which reacts with alkenes leading to a cyclic
sulfonium ion C upon releasing arylsulfenyl iodide (ArSI). The
in situ generated ArSI can further transfer a second equivalent of
electrophilic sulfide to alkenes affording a cyclic sulfonium ion
C. The cyclic sulfonium ion intermediate C reacts with an acetate
anion in two pathways (SN1 or SN2). With the styrene derivatives
(R = Aryl), the SN1 mechanism operates and the corresponding
1,2-acetoxysulfide 3 was observed as a single isomer. In contrast,
the acetate anion nonselectively reacts with the cyclic sulfonium
ion C derived from aliphatic alkenes (R = Alkyl) leading to 1,2-
acetoxysulfide 7 (via an SN2 mechanism) or 1,2-acetoxysulfide 7'
(via an SN1 mechanism). The results obtained when cyclohexene
(6f) being used as an alkene substrate supported the formation of
the cyclic sulfonium intermediate. The acetate anion then
attacked the cyclic sulfonium ion derived from cyclohexene
affording the corresponding 1,2-acetoxysulfide 7 as a single
isomer (trans).
4.2.1. 1-(4-Bromophenyl)-2-(phenylthio)ethyl acetate (3aa). p-
Bromostyrene (1a) (94 mg, 0.51 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3aa (147
mg, 82%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.38;
IR (neat): νmax 1742, 1228 cm-1; H NMR (300 MHz, CDCl3): δ
1
7.49 (br d, J = 8.4 Hz, 2H, ArH), 7.40 (br d, J = 7.0 Hz, 2H, ArH),
7.34–7.28 (m, 2H, ArH), 7.28–7.21 (m, 3H, ArH), 5.86 (dd, J =
7.6, 5.9 Hz, 1H, ArCH), 3.43 (dd, J = 13.9, 7.6 Hz, 1H, CHH),
3.23 (dd, J = 13.9, 5.9 Hz, 1H, CHH), 2.05 (s, 3H, CH3); 13C
NMR (75 MHz, CDCl3): δ 169.8, 137.8, 135.1, 131.6, 130.1,
128.9, 128.3, 126.6, 122.3, 73.9, 39.7, 20.8; HRMS (ESI-TOF):
MNa+, found: 372.9871 (97); error = 1 ppm, 374.9850 (100);
error = 1 ppm. requires C16H15BrNaO2S 372.9874, 374.9853.
PhI(OAc)2
+
I-
PhI + OAc- + AcOI
A
O
I
O
CH3
I
A
S
Ar
S
Ar
Ar
S
Ar
S
2
B
OAc
R = Aryl
SN
I
SAr
Ar
4.2.2. 1-Phenyl-2-(phenylthio)ethyl acetate (3ba).12 Styrene (1b)
(52 mg, 0.50 mmol). Column chromatography (silica gel; 2%
EtOAc/hexanes) yields 3ba (116 mg, 85%); colorless viscous oil;
Rf (10% EtOAc/hexanes) 0.36; IR (neat): νmax 1743, 1249, 1231
1
R
S
Ar
S
R
3 (single isomer)
Ar
S
R
OAc-
C
-ArSI
OAc
SAr
B
R = Alkyl
SAr
OAc
R
R
R
7' (minor; via SN1)
7 (major; via SN2)
1
cm-1; H NMR (300 MHz, CDCl3): δ 7.49–7.24 (m, 10H, ArH),
6.00 (dd, J = 8.0, 5.4 Hz, 1H, ArCH), 3.50 (dd, J = 13.9, 8.0 Hz,
1H, CHH), 3.32 (dd, J = 13.9, 5.4 Hz, 1H, CHH), 2.08 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): δ 169.8, 138.8, 135.4, 129.9,
128.8, 128.4, 128.2, 126.4, 126.3, 74.4, 39.8, 20.8; HRMS (ESI-
Scheme 1 A plausible reaction mechanism.
3. Conclusions
TOF): MNa+, found: 295.0753; error
C16H16NaO2S 295.0769.
= 5 ppm. requires
In summary, we demonstrated a facile synthesis of 1,2-
acetoxysulfides by using (diacetoxyiodo)benzene (PhI(OAc)2)/KI
to promote the reaction of alkenes with diaryl disulfides. The
method is simple, enables the use of both organosulfur groups of
the disulfide, fast, and being conducted under non-anhydrous
conditions.
4.2.3. 1-(4-Chlorophenyl)-2-(phenylthio)ethyl acetate (3ca). p-
Chlorostyrene (1c) (69 mg, 0.50 mmol). Column chromatography
(silica gel; 2% EtOAc/hexanes) yields 3ca (126 mg, 82%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.39; IR (neat):
1
νmax 1740, 1232 cm-1; H NMR (300 MHz, CDCl3): δ 7.30–7.08
4. Experimental section
(m, 9H, ArH), 5.74 (dd, J = 7.6, 5.8 Hz, 1H, ArCH), 3.30 (dd, J =
13.9, 7.6 Hz, 1H, CHH), 3.10 (dd, J = 13.9, 5.8 Hz, 1H, CHH), 1.92
(s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ 169.8, 137.3, 135.2,
134.1, 130.1, 129.0, 128.6, 128.0, 126.6, 73.9, 39.8, 20.9; HRMS
(ESI-TOF): MNa+, found: 329.0372 (100); error = 2 ppm,
331.0346 (36); error = 1 ppm. requires C16H15ClNaO2S 329.0379,
331.0349.
4.1. General
The 1H and 13C NMR spectra were recorded on Bruker DPX-
300 (300 MHz) spectrometer, Bruker Ascend™ 400 (400 MHz)
or Bruker Advance-500 (500 MHz) in CDCl3. 1H NMR chemical
shifts are reported in ppm using tetramethylsilane (TMS) as an
internal standard. 13C NMR chemical shifts are reported in ppm
with residual non-deuterated solvent peak as an internal standard.
NMR data are reported as follow: 1H NMR chemical shifts,
measured in parts per million (ppm) down field from
tetramethylsilane (TMS) signal (δ), proton count, multiplicity,
observed coupling constant (J) in Hertz (Hz). Multiplicities are
reported as singlet (s), broad (br), doublet (d), doublet of doublets
(dd), doublet of triplets (dt), triplet (t) and multiplet (m). The IR
4.2.4. 1-(4-Fluorophenyl)-2-(phenylthio)ethyl acetate (3da). p-
Fluorostyrene (1d) (62 mg, 0.50 mmol). Column chromatography
(silica gel; 2% EtOAc/hexanes) yields 3da (116 mg, 79%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.33; IR (neat):
νmax 1743, 1223 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.40 (d, J =
7.5 Hz, 2H, ArH), 7.35–7.20 (m, 5H, ArH), 7.04 (t, J = 8.5 Hz,
2H, ArH), 5.89 (dd, J = 7.5, 5.7 Hz, 1H, ArCH), 3.43 (dd, J =
13.8, 7.5 Hz, 1H, CHH), 3.23 (dd, J = 13.8, 5.7 Hz, 1H, CHH),
2.03 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ 169.8, 162.5 (d,
J = 245.7 Hz), 135.3, 134.7 (d, J = 3.2 Hz), 130.1, 128.9, 128.4
(d, J = 8.3 Hz), 126.6, 115.3 (d, J = 21.5 Hz), 73.9, 39.8, 20.8;
HRMS (ESI-TOF): MNa+, found: 313.0671; error = 1 ppm.
requires C16H15FNaO2S 313.0674.
spectra were recorded
a Perkin Elmer EX FI-IR system
spectrometer. The high resolution mass spectra were recorded
using a Bruker Micro TOF spectrometer at Faculty of Science,
Mahidol University. Melting points (mp) were determined on an
Electrothermal IA 9000 series apparatus and are uncorrected.
4.2. Synthesis of 1,2-acetoxysulfide derived from styrene derivatives

ACCEPTED MANUSCRIPT
5
4.2.5. 2-(Phenylthio)-1-(p-tolyl)ethyl acetate (3ea).12 p-
Methylstyrene (1e) (62 mg, 0.53 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3ea (107
mg, 71%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.37;
(silica gel; 2% EtOAc/hexanes) yields 3ja (99 mg, 68%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.36; IR (neat):
νmax 1742, 1272, 1227 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.43–
7.20 (m, 6H, ArH), 7.13–6.97 (m, 3H, ArH), 5.89 (dd, J = 7.5,
5.6 Hz, 1H, ArCH), 3.41 (dd, J = 13.8, 7.5 Hz, 1H, CHH), 3.24 (dd,
J = 13.8, 5.6 Hz, 1H, CHH), 2.05 (s, 3H, CH3); 13C NMR (75 MHz,
CDCl3): δ 169.8, 162.7 (d, J = 245.3 Hz), 141.4 (d, J = 7.0 Hz),
135.2, 130.2, 130.0 (d, J = 8.2 Hz), 129.0, 126.7, 122.3 (d, J = 2.9
Hz), 115.2 (d, J = 21.0 Hz), 113.5 (d, J = 22.1 Hz), 73.8 (d, J = 1.7
Hz), 39.9, 20.8; HRMS (ESI-TOF): MNa+, found: 313.0672; error
= 1 ppm. requires C16H15FNaO2S 313.0674.
1
IR (neat): νmax 1742, 1238 cm-1; H NMR (300 MHz, CDCl3): δ
7.29 (d, J = 7.2 Hz, 2H, ArH), 7.24–7.01 (m, 7H, ArH), 5.77 (dd,
J = 8.0, 5.6 Hz, 1H, ArCH), 3.32 (dd, J = 13.8, 8.0 Hz, 1H, CHH),
3.13 (dd, J = 13.8, 5.6 Hz, 1H, CHH), 2.25 (s, 3H, ArCH3), 1.92 (s,
3H, ArCH3); 13C NMR (75 MHz, CDCl3): δ 170.0, 138.2, 135.9,
135.6, 130.0, 129.2, 128.9, 126.6, 126.4, 74.4, 39.8, 21.1, 21.0;
HRMS (ESI-TOF): MNa+, found: 309.0922; error = 1 ppm.
requires C17H18NaO2S 309.0925.
4.2.11. 1-(3-Formylphenyl)-2-(phenylthio)ethyl acetate (3ka). m-
Vinylbenzaldehyde (1k) (67 mg, 0.51 mmol). Column
chromatography (silica gel; 10% EtOAc/hexanes) yields 3ka (95
mg, 63%); light yellow viscous oil; Rf (10% EtOAc/hexanes)
4.2.6. 1-(4-(Chloromethyl)phenyl)-2-(phenylthio)ethyl acetate (3fa)
p-Vinylbenzyl chloride (1f) (77 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3fa (125
mg, 78%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.30;
0.18; IR (neat): νmax 2730, 1744, 1699, 1229 cm-1; H NMR (300
1
1
IR (neat): νmax 1740, 1232 cm-1; H NMR (300 MHz, CDCl3): δ
MHz, CDCl3): δ 10.00 (s, 1H, CHO), 7.88–7.80 (m, 2H, ArH),
7.60 (d, J = 7.7 Hz, 1H, ArH), 7.51 (dd, J = 7.7, 7.5 Hz, 1H,
ArH), 7.37 (br d, J = 7.2 Hz, 1H, ArH), 7.33–7.18 (m, 3H, ArH),
5.95 (dd, J = 7.5, 5.9 Hz, 1H, ArCH), 3.45 (dd, J = 14.0, 7.5 Hz,
1H, CHH), 3.27 (dd, J = 14.0, 5.9 Hz, 1H, CHH), 2.05 (s, 3H, CH3);
13C NMR (75 MHz, CDCl3): δ 191.7, 169.8, 140.0, 136.5, 135.0,
132.7, 130.2, 129.7 , 129.1, 129.0, 127.4, 126.7, 73.9, 39.7, 20.8;
HRMS (ESI-TOF): MNa+, found: 323.0719; error = 0.3 ppm.
requires C17H16NaO3S 323.0718.
7.30–7.10 (m, 9H, ArH), 5.79 (dd, J = 7.8, 5.6 Hz, 1H, ArCH), 4.48
(s, 2H, ArCH2Cl), 3.32 (dd, J = 13.9, 7.8 Hz, 1H, CHH), 3.14 (dd, J
= 13.9, 5.6 Hz, 1H, CHH), 1.94 (s, 3H, CH3); 13C NMR (75 MHz,
CDCl3): δ 169.9, 139.2, 137.6, 135.3, 130.1, 129.0, 128.7, 127.0,
126.6, 74.2, 45.7, 39.9, 20.9; HRMS (ESI-TOF): MNa+, found:
343.0535 (100); error = 0 ppm, 345.0515 (36); error = 3 ppm.
requires C17H17ClNaO2S 343.0535, 345.0506.
4.2.7. 4-(1-Acetoxy-2-(phenylthio)ethyl)phenyl acetate (3ga). p-
Acetoxystyrene (1g) (82 mg, 0.51 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3ga (135
mg, 82%); light yellow viscous oil; Rf (20% EtOAc/hexanes)
4.2.12. 1-(3-Nitrophenyl)-2-(phenylthio)ethyl acetate (3la). m-
Nitrostyrene (1l) (75 mg, 0.51 mmol). Column chromatography
(silica gel; 5% EtOAc/hexanes) yields 3la (109 mg, 69%); light
yellow viscous oil; Rf (10% EtOAc/hexanes) 0.19; IR (neat): νmax
1745, 1530, 1351, 1226 cm-1; 1H NMR (300 MHz, CDCl3): δ 8.12–
8.03 (m, 2H, ArH), 7.56 (d, J = 7.4 Hz, 2H, ArH), 7.42 (t, J = 8.0
Hz, 1H, ArH), 7.22–7.13 (m, 5H, ArH), 5.85 (dd, J = 7.0, 6.4 Hz,
1H, ArCH), 3.36 (dd, J = 14.1, 7.0 Hz, 1H, CHH), 3.17 (dd, J =
14.1, 6.4 Hz, 1H, CHH), 1.96 (s, 3H, CH3); 13C NMR (75 MHz,
CDCl3): δ 169.7, 148.2, 140.8, 134.7, 133.0, 130.4, 129.4, 129.1,
126.9, 123.3, 121.7, 73.6, 39.7, 20.8; HRMS (ESI-TOF): MNa+,
found: 340.0606; error = 4 ppm. requires C16H15NNaO4S
340.0619.
1
0.33; IR (neat): νmax 1745, 1216, 1198 cm-1; H NMR (300 MHz,
CDCl3): δ 7.41–7.18 (m, 7H, ArH), 7.08 (br d, J = 8.8 Hz, 2H,
ArH), 5.90 (dd, J = 7.9, 5.4 Hz, 1H, ArCH), 3.41 (dd, J = 13.9,
7.9 Hz, 1H, CHH), 3.23 (dd, J = 13.9, 5.4 Hz, 1H, CHH), 2.30
(s, 3H, CH3), 2.02 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ
169.8, 169.2, 150.5, 136.4, 135.3, 130.1, 128.9, 127.8, 126.5,
121.6, 73.9, 39.9, 21.0, 20.9; HRMS (ESI-TOF): MNa+, found:
353.0823; error = 0 ppm. requires C18H18NaO4S 353.0823.
4.2.8. 1-(4-Methoxyphenyl)-2-(phenylthio)ethyl acetate (3ha). p-
Vinylanisole (1h) (69 mg, 0.5 mmol) Column chromatography
(silica gel; 5% EtOAc/hexanes) yields 3ha (49 mg, 33%);
colorless viscous oil; Rf (20% EtOAc/hexanes) 0.29; IR (neat):
4.2.13. 1-(2-Chlorophenyl)-2-(phenylthio)ethyl acetate (3ma). o-
Chlorostyrene (1m) (70 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3ma (115
mg, 76%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.34;
IR (neat): νmax 1747, 1244, 1226 cm-1; 1H NMR (300 MHz, CDCl3):
δ 7.47–7.43 (m, 3H, ArH), 7.36–7.22 (m, 6H, ArH), 6.33 (dd, J =
8.1, 4.4 Hz, 1H, ArCH), 3.40 (dd, J = 14.0, 4.4 Hz, 1H, CHH), 3.13
(dd, J = 14.0, 8.1 Hz, 1H, CHH), 2.05 (s, 3H, CH3); 13C NMR (75
MHz, CDCl3): δ 169.6, 136.7, 135.4, 132.2, 130.4, 129.6, 129.2,
128.8, 127.3, 127.0, 126.6, 71.3, 38.9, 20.7; HRMS (ESI-TOF):
MNa+, found: 329.0377 (100); error = 1 ppm, 331.0354 (36);
error = 2 ppm. requires C16H15ClNaO2S 329.0379, 331.0349.
1
νmax 2836, 1740, 1243 cm-1; H NMR (300 MHz, CDCl3): δ 7.41
(d, J = 7.0 Hz, 2H, ArH), 7.37–7.20 (m, 5H, ArH), 6.90 (d, J = 8.7
Hz, 2H, ArH), 5.88 (dd, J = 7.9, 5.9 Hz, 1H, ArCH), 3.82 (s, 3H,
OCH3), 3.46 (dd, J = 13.8, 7.9 Hz, 1H, CHH), 3.25 (dd, J = 13.8, 5.9
Hz, 1H, CHH), 2.04 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ
170.0, 159.6, 135.6, 131.0, 130.0, 128.9, 128.1, 126.4, 113.9, 74.3,
55.2, 39.8, 21.0; HRMS (ESI-TOF): MNa+, found: 325.0872;
error = 1 ppm. requires C17H18NaO3S 325.0874.
4.2.9. 1-(3-Chlorophenyl)-2-(phenylthio)ethyl acetate (3ia). m-
Chlorostyrene (1i) (69 mg, 0.50 mmol). Column chromatography
(silica gel; 2% EtOAc/hexanes) yields 3ia (116 mg, 75%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.36; IR (neat):
νmax 1745, 1226 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.40 (br d, J
= 7.6 Hz, 2H, ArH), 7.37–7.18 (m, 7H, ArH), 5.85 (dd, J = 7.6,
5.6 Hz, 1H, ArCH), 3.40 (dd, J = 14.0, 7.6 Hz, 1H, CHH), 3.22
(dd, J = 14.0, 5.6 Hz, 1H, CHH), 2.04 (s, 3H, CH3); 13C NMR
(75 MHz, CDCl3): δ 169.8, 140.9, 135.2, 134.4, 130.3, 129.8,
129.0, 128.5, 126.73, 126.70, 124.9, 73.9, 39.9, 20.9; HRMS
(ESI-TOF): MNa+, found: 329.0395 (100); error = 5 ppm,
4.2.14. 1-(4-Bromophenyl)-2-(p-tolylthio)ethyl acetate (3ab). p-
Bromostyrene (1a) (92 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3ab (156
o
mg, 85%); white solid; mp = 70.5−72.0 C (EtOAc/hexanes); Rf
(10% EtOAc/hexanes) 0.39; IR (KBr): νmax 1741, 1237, 1211 cm-1;
1H NMR (300 MHz, CDCl3): δ 7.34 (br d, J = 8.4 Hz, 2H, ArH),
7.17 (br d, J = 8.1 Hz, 2H, ArH), 7.08 (br d, J = 8.4 Hz, 2H,
ArH), 6.99 (d, J = 8.1 Hz, 2H, ArH), 5.69 (dd, J = 7.7, 5.8 Hz,
1H, ArCH), 3.23 (dd, J = 13.9, 7.7 Hz, 1H, CHH), 3.04 (dd, J =
13.9, 5.8 Hz, 1H, CHH), 2.22 (s, 3H, ArCH3), 1.92 (s, 3H, CH3);
13C NMR (75 MHz, CDCl3): δ 169.8, 137.9, 136.9, 131.5, 131.3,
130.9, 129.7, 128.3, 122.2, 73.8, 40.4, 20.93, 20.86; HRMS (ESI-
TOF): MNa+, found: 387.0013 (92); error = 4 ppm, 388.9992
331.0367 (38); error = 5 ppm.
329.0379, 331.0349.
requires C16H15ClNaO2S
4.2.10. 1-(3-Fluorophenyl)-2-(phenylthio)ethyl acetate (3ja). m-
Fluorostyrene (1j) (61 mg, 0.50 mmol). Column chromatography

ACCEPTED MANUSCRIPT
6
Tetrahedron
(100); error = 5 ppm. requires C17H17BrNaO2S 387.0030,
(dd, J = 14.0, 5.9 Hz 1H, CHH), 2.30 (s, 3H, CH3), 2.04 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): δ 191.6, 169.7, 140.1, 136.9,
136.5, 132.7, 131.2, 131.0, 129.7, 129.6, 129.1, 127.5, 73.9, 40.4,
20.9, 20.8; HRMS (ESI-TOF): MNa+, found: 337.0875; error =
0.2 ppm. requires C18H18NaO3S 337.0874.
389.0010.
4.2.15. 1-(4-Chlorophenyl)-2-(p-tolylthio)ethyl acetate (3cb) p-
Chlorostyrene (1c) (70 mg, 0.51 mmol). Column chromatography
(silica gel; 2% EtOAc/hexanes) yields 3cb (143 mg, 88%); white
solid; mp
=
58.0−59.0 oC (EtOAc/hexanes); Rf (10%
4.2.20. 1-(2-Chlorophenyl)-2-(p-tolylthio)ethyl acetate (3mb). o-
Chlorostyrene (1m) (69 mg, 0.50 mmol), Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3mb (133
mg, 84%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.42;
IR (neat): νmax 1747, 1244, 1225 cm-1; 1H NMR (300 MHz, CDCl3):
δ 7.48 (dd, J = 7.4, 2.0 Hz, 1H, ArH), 7.43–7.21 (m, 5H, ArH),
7.14 (d, J = 7.9 Hz, 2H, ArH), 6.34 (dd, J = 8.2, 4.1 Hz, 1H,
ArCH), 3.38 (dd, J = 14.2, 4.1 Hz, 1H, CHH), 3.27 (dd, J = 14.2, 8.2
Hz, 1H, CHH), 2.36 (s, 3H, ArCH3), 2.09 (s, 3H, CH3); 13C NMR
(75 MHz, CDCl3): δ 169.5, 136.8, 136.7, 132.1, 131.5, 131.1,
129.6, 129.5, 129.1, 127.2, 126.9, 71.3, 39.5, 20.9, 20.7; HRMS
(ESI-TOF): MNa+, found: 343.0536 (100); error = 0.2 ppm,
345.0491 (29); error = 5 ppm. requires C17H17ClNaO2S 343.0535,
345.0507.
EtOAc/hexanes) 0.42; IR (KBr): νmax 1740, 1238, 1210 cm-1; H
NMR (300 MHz, CDCl3): δ 7.22–7.12 (m, 6H, ArH), 7.00 (d, J =
8.0 Hz, 2H, ArH), 5.71 (dd, J = 7.7, 5.8 Hz, 1H, ArCH), 3.24 (dd,
J = 13.9, 7.7 Hz, 1H, CHH), 3.05 (dd, J = 13.9, 5.8 Hz, 1H,
CHH), 2.22 (s, 3H, ArCH3), 1.92 (s, 3H, CH3); 13C NMR (75
MHz, CDCl3): δ 169.8, 137.4 , 136.9, 134.1, 131.3, 130.9, 129.7 ,
128.6, 128.0, 73.8, 40.5, 20.9, 20.9; HRMS (ESI-TOF): MNa+,
found: 343.0532 (100); error = 1 ppm, 345.0507 (36); error = 0.2
ppm. requires C17H17ClNaO2S 343.0535, 345.0506.
1
4.2.16. 1-(4-Fluorophenyl)-2-(p-tolylthio)ethyl acetate (3db). p-
Fluorostyrene (1d) (70 mg, 0.51 mmol). Column chromatography
(silica gel; 2% EtOAc/hexanes) yields 3db (134 mg, 88%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.38; IR (neat):
νmax 1744, 1225 cm-1; H NMR (300 MHz, CDCl3): δ 7.22–7.12
1
4.2.21. 1-(4-Bromophenyl)-2-((4-methoxyphenyl)thio)ethyl acetate
(3ac). p-Bromostyrene (1a) (93 mg, 0.51 mmol). Column
chromatography (silica gel; 3–7% EtOAc/hexanes) yields 3ac
(m, 4H, ArH), 6.99 (d, J = 8.0 Hz, 2H, ArH), 6.90 (br t, J = 8.7 Hz,
2H, ArH), 5.72 (dd, J = 7.8, 5.8 Hz, 1H, ArCH), 3.25 (dd, J = 13.9,
7.8 Hz, 1H, CHH), 3.05 (dd, J = 13.9, 5.8 Hz, 1H, CHH), 2.21 (s,
3H, ArCH3), 1.91 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ
169.8, 162.5 (d, J = 245.6 Hz), 136.8, 134.8 (d, J = 3.2 Hz),
131.4, 130.9, 129.7, 128.4 (d, J = 8.3 Hz), 115.3 (d, J = 21.5 Hz),
73.8, 40.5, 20.9, 20.9; HRMS (ESI-TOF): MNa+, found:
327.0830; error = 0.3 ppm. requires C17H17FNaO2S 327.0831.
(169 mg, 88%); white solid; mp
=
73.0−74.0 oC
(EtOAc/hexanes); Rf (10% EtOAc/hexanes) 0.42; IR (KBr): νmax
1747, 1251, 1236, 1212 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.43
(d, J = 8.4 Hz, 2H, ArH), 7.34 (br d, J = 8.8 Hz, 2H, ArH), 7.16
(d, J = 8.4, 2H, ArH), 6.83 (d, J = 8.8 Hz, 2H, ArH), 5.77 (dd, J
= 7.8, 5.7 Hz, 1H, ArCH), 3.78 (s, 3H, OCH3), 3.27 (dd, J = 13.9,
7.8 Hz, 1H, CHH), 3.09 (dd, J = 13.9, 5.7 Hz, 1H, CHH), 2.03 (s,
3H, CH3); 13C NMR (75 MHz, CDCl3): δ 169.8, 159.2, 137.9,
133.8, 131.5, 128.3, 125.2, 122.1, 114.6, 73.8, 55.2, 41.6, 20.9;
HRMS (ESI-TOF): MNa+, found: 402.9976 (99); error = 1 ppm,
4.2.17. 1-(4-Methoxyphenyl)-2-(p-tolylthio)ethyl acetate (3hb). p-
Vinylanisole (1h) (69 mg, 0.50 mmol). Column chromatography
(silica gel; 20% diethyl ether/hexanes) yields 3hb (92 mg, 58%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.42; IR (neat):
νmax 1740, 1241 cm-1; H NMR (300 MHz, CDCl3): δ 7.22–7.12
1
404.9955 (100); error
402.9979, 404.9959.
= 1 ppm. requires C17H17BrNaO3S
(m, 4H, ArH), 7.08 (br d, J = 7.9 Hz, 2H, ArH), 6.86 (dd, J = 6.6,
2.1 Hz, 1H, ArH), 5.80 (dd, J = 7.9, 5.7 Hz, 1H, ArCH), 3.78 (s,
3H, OCH3), 3.36 (dd, J = 13.8, 7.9 Hz, 1H, CHH), 3.16 (dd, J =
13.8, 5.7 Hz, 1H, CHH), 2.32 (s, 3H, ArCH3), 2.01 (s, 3H,
CH3);13C NMR (75 MHz, CDCl3): δ 170.1, 159.6, 136.8, 131.8,
131.1, 130.9, 129.8, 128.1, 113.9, 74.3, 55.3, 40.6, 21.1, 21.0;
HRMS (ESI-TOF): MNa+, found: 339.1031; error = 0 ppm.
requires C18H20NaO3S 339.1031.
4.2.22. 1-(4-Chlorophenyl)-2-((4-methoxyphenyl)thio)ethyl acetate
(3cc). p-Chlorostyrene (1c) (70 mg, 0.50 mmol). Column
chromatography (silica gel; 3–7% EtOAc/hexanes) yields 3ac
(131 mg, 81%); colorless viscous oil; Rf (10% EtOAc/hexanes)
0.24; IR (neat): νmax 1739, 1245 cm-1; 1H NMR (300 MHz,
CDCl3): δ 7.39–7.23 (m, 6H, ArH), 6.86 (br d, J = 8.9 Hz, 2H,
ArH), 5.81 (dd, J = 7.8, 5.7 Hz, 1H, ArCH), 3.82 (s, 3H, OCH3),
3.30 (dd, J = 13.9, 7.8 Hz, 1H, CHH), 3.12 (dd, J = 13.9, 5.7 Hz,
1H, CHH), 2.06 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ
169.9, 159.3, 137.5, 134.0, 133.9, 128.6, 128.1, 125.2, 114.6,
73.8, 55.3, 41.7, 21.0; HRMS (ESI-TOF): MNa+, found:
359.0485 (100); error = 0 ppm, 361.0462 (35); error = 2 ppm.
requires C17H17ClNaO3S 359.0485, 361.0455.
4.2.18. 1-(3-Chlorophenyl)-2-(p-tolylthio)ethyl acetate (3ib). m-
Chlorostyrene (1i) (69 mg, 0.50 mmol). Column chromatography
(silica gel; 2% EtOAc/hexanes) yields 3ib (128 mg, 81%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.41; IR (neat):
νmax 1747, 1227 cm-1; H NMR (300 MHz, CDCl3): δ 7.24–7.13
1
(m, 5H, ArH), 7.13–7.05 (m, 1H, ArH), 7.01 (d, J = 7.9 Hz, 2H,
ArH), 5.70 (dd, J = 7.9, 5.6 Hz, 1H, ArCH), 3.23 (dd, J = 14.0,
7.9 Hz, 1H, CHH) 3.06 (dd, J = 14.0, 5.6 Hz, 1H, CHH), 2.23 (s,
3H, ArCH3), 1.94 (s, 3H, CH3).13C NMR (75 MHz, CDCl3): δ
169.8, 141.0, 137.0, 134.4 , 131.3, 131.1, 129.8, 129.7, 128.4,
126.7, 124.9, 73.8, 40.6, 21.0, 20.9; HRMS (ESI-TOF): MNa+,
found: 343.0536 (100); error = 0.2 ppm, 345.0503 (35); error = 1
ppm. requires C17H17ClNaO2S 343.0535, 345.0507.
4.2.23. 1-(4-Fluorophenyl)-2-((4-methoxyphenyl)thio)ethyl acetate
(3dc). p-Fluorostyrene (1d) (61 mg, 0.50 mmol). Column
chromatography (silica gel; 3–7% EtOAc/hexanes) yields 3dc
(137 mg, 86%); colorless viscous oil; Rf (10% EtOAc/hexanes)
0.23; IR (neat): νmax 1743, 1246, 1225; 1H NMR (300 MHz,
CDCl3): δ 7.38 (br d, J = 8.9 Hz, 2H, ArH), 7.35–7.26 (m, 2H,
ArH), 7.03 (br t, J = 8.7 Hz, 2H, ArH), 6.87 (br d, J = 8.9 Hz,
2H, ArH), 5.83 (dd, J = 7.9, 5.7 Hz, 1H, ArCH), 3.81 (s, 3H,
OCH3), 3.31 (dd, J = 13.9, 7.9 Hz, 1H, CHH), 3.12 (dd, J = 13.9,
5.7 Hz, 1H, CHH), 2.06 (s, 3H, CH3); 13C NMR (75 MHz,
CDCl3): δ 169.9, 162.4 (d, J = 245.6 Hz), 159.2, 134.8 (d, J = 3.2
Hz), 133.8, 128.4 (d, J = 8.2 Hz), 125.3, 115.3 (d, J = 21.4 Hz),
114.6, 73.8, 55.2, 41.8, 20.9; HRMS (ESI-TOF): MNa+, found:
343.0782; error = 1 ppm. requires C17H17FNaO3S 343.0780.
4.2.19. 1-(3-Formylphenyl)-2-(p-tolylthio)ethyl acetate (3kb). m-
Vinylbenzaldehyde (1k) (67 mg, 0.50 mmol). Column
chromatography (silica gel; 2–8% EtOAc/hexanes) yields 3kd
(115 mg, 72%); light yellow viscous oil; Rf (10% EtOAc/hexanes)
0.36; IR ( neat): νmax 1744, 1699, 1230 cm-1; H NMR (300 MHz,
1
CDCl3): δ 9.97 (s, 1 H, CHO), 7.84–7.76 (m, 2H, ArH), 7.57 (dt, J
= 7.6, 1.5 Hz, 1H, ArH), 7.48 (t, J = 7.6 Hz, 1H, ArH), 7.27 (br d, J
= 8.0 Hz, 2H, ArH), 7.08 (br d, J = 8.0 Hz, 2H, ArH), 5.90 (dd, J =
7.5, 5.9 Hz, 1H, ArCH), 3.38 (dd, J = 14.0, 7.5 Hz 1H, CHH), 3.20
4.2.24 1-(3-Chlorophenyl)-2-((4-methoxyphenyl)thio)ethyl acetate
(3ic). m-Chlorostyrene (1i) (69 mg, 0.50 mmol). Column

ACCEPTED MANUSCRIPT
7
chromatography (silica gel; 3–7% EtOAc/hexanes) yields 3ic
(142 mg, 78%); colorless viscous oil; Rf (10% EtOAc/hexanes)
0.24; IR (neat): νmax 1744, 1245 cm-1; 1H NMR (300 MHz,
CDCl3): δ 7.35 (br d, J = 8.9 Hz, 2H, ArH), 7.30–7.13 (m, 4H,
ArH), 6.83 (d, J = 8.9 Hz, 2H, ArH), 5.77 (dd, J = 8.0, 5.4 Hz,
1H, ArCH), 3.25 (s, 3H, OCH3), 3.08 (dd, J = 14.0, 8.0 Hz, 1H,
CHH), 3.12 (dd, J = 14.0, 5.4 Hz, 1H, CHH), 2.04 (s, 3H, CH3);
13C NMR (75 MHz, CDCl3): δ 169.8, 159.3, 141.0, 134.3, 134.0,
129.7, 128.4, 126.7, 125.1, 124.9, 114.6, 73.7, 55.2, 41.8, 20.9;
HRMS (ESI-TOF): MNa+, found: 359.0485 (100); error = 0 ppm,
361.0469 (33); error = 4 ppm. requires C17H17ClNaO3S 359.0485,
361.0455.
= 14.0, 7.7 Hz, CHH), 3.17 (dd, J = 14.0, 5.7 Hz, 1H, CHH), 2.06
(s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ 169.8, 162.0 (d, J =
246.0 Hz), 137.2, 134.2, 133.2 (d, J = 8.1 Hz), 130.1 (d, J = 3.4
Hz), 128.6, 128.0, 116.1 (d, J = 21.8 Hz), 73.7, 41.0, 20.9; HRMS
(ESI-TOF): MNa+, found: 347.0279 (100); error = 2 ppm,
349.0251 (35); error
347.0285, 349.0255.
= 1 ppm. requires C16H14ClFNaO2S
4.2.29. 1-(4-Fluorophenyl)-2-((4-fluorophenyl)thio)ethyl acetate
(3dd). p-Fluorostyrene (1d) (61 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3dd (123
mg, 80%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.32;
IR (neat): νmax 1744, 1225 cm-1; H NMR (500 MHz, CDCl3): δ
1
4.2.25. 1-(3-Formylphenyl)-2-((4-methoxyphenyl)thio)ethyl acetate
(3kc). m-Vinylbenzaldehyde (1k) (67 mg, 0.50 mmol). Column
chromatography (silica gel; 5–12% EtOAc/hexanes) yields 3kc
(119 mg, 72%); light yellow viscous oil; Rf (20% EtOAc/ hexanes)
7.46–7.37 (m, 2H, ArH), 7.32–7.28 (m, 2H, ArH), 7.06–7.00 (m,
4H, ArH), 5.85 (dd, J = 7.8, 5.8 Hz, 1H, ArCH), 3.37 (dd, J =
14.0, 7.8 Hz, 1H, CHH), 3.17 (dd, J = 14.0, 5.8 Hz, 1H, CHH),
2.06 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3): δ 169.8, 162.6
(d, J = 245.9 Hz), 162.1 (d, J = 245.8 Hz), 134.6, 133.2 (d, J =
8.0 Hz), 130.2, 128.5 (d, J = 8.1 Hz), 116.1 (d, J = 21.8 Hz),
115.4 (d, J = 21.6 Hz), 73.8, 41.1, 20.8; HRMS (ESI-TOF):
1
0.26; IR (neat): νmax 2730, 1743, 1699, 1246 cm-1; H NMR (300
MHz, CDCl3): δ 9.98 (s, 1H, CHO), 7.82–7.76 (m, 2H, ArH), 7.56
(dt, J = 7.8, 1.5 Hz, 1H, ArH), 7.49 (br t, J = 7.8 Hz, 1H, ArH), 7.34
(br d, J = 8.8 Hz, 2H, ArH), 6.83 (br d, J = 8.8 Hz, 2H, ArH), 5.88
(dd, J = 7.7, 5.8 Hz, 1H, ArCH), 3.78 (s, 3H, OCH3), 3.32 (dd, J =
14.0, 7.7 Hz, 1H, CHH), 3.14 (dd, J = 14.0, 5.8 Hz, 1H, CHH), 2.06
(s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ 191.8, 169.8, 159.2
140.2, 136.4, 133.9, 132.7, 129.7, 129.1, 127.5, 125.0, 114.6
73.8, 55.2, 41.7, 20.9; HRMS (ESI-TOF): MNa+, found:
353.0834; error = 3 ppm. requires C18H18NaO4S 353.0823.
MNa+, found: 331.0579; error
C16H14F2NaO2S 331.0580.
=
0.3 ppm. requires
4.2.30. 2-((4-Fluorophenyl)thio)-1-(4-methoxyphenyl)ethyl acetate
(3hd). p-Vinylanisole (1h) (67 mg, 0.50 mmol). Column
chromatography (silica gel; 5% EtOAc/hexanes) yields 3hd (37
mg, 23%); pale yellow solid; mp
=
43.0−44.0 oC
(EtOAc/hexanes); Rf (10% EtOAc/hexanes) 0.34; IR (KBr): νmax
2838, 1737, 1229 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.39 (dd, J
= 8.8, 5.2 Hz, 2H, ArH), 7.26 (br d, J = 8.7 Hz, 2H, ArH), 7.01 (br
t, J = 8.8 Hz, 2H, ArH), 6.89 (d, J = 8.7 Hz, 2H, ArH), 5.83 (dd, J
= 7.9, 5.8 Hz, 1H, ArH), 3.82 (s, 3H, OCH3), 3.38 (dd, J = 13.8, 7.9
Hz, 1H, CHH), 3.23 (dd, J = 13.8, 5.8 Hz, 1H, CHH), 2.05 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): δ 170.0, 162.0 (d, J = 245.6
Hz), 159.6, 133.1 (d, J = 8.0 Hz), 130.8, 130.4 (d, J = 3.4 Hz),
128.1, 116.1 (d, J = 21.8 Hz), 113.9, 74.2, 55.2, 41.0, 21.0; HRMS
(ESI-TOF): MNa+, found: 343.0781; error = 0.2 ppm. requires
C17H17FNaO3S 343.0780.
4.2.26. 1-(2-Chlorophenyl)-2-((4-methoxyphenyl)thio)ethyl acetate
(3mc). o-Chlorostyrene (1m) (69 mg, 0.50 mmol). Column
chromatography (silica gel; 2–7% EtOAc/hexanes) yields 3mc
(142 mg, 84%); colorless viscous oil; Rf (10% EtOAc/hexanes)
0.25; IR (neat): νmax 1745, 1246 cm-1; 1H NMR (300 MHz,
CDCl3): δ 7.46–7.40 (m, 3H, ArH), 7.34–7.19 (m, 3H, ArH),
6.86 (br d, J = 8.9 Hz, 2H, ArH), 6.28 (dd, J = 8.4, 4.0 Hz, 1H,
ArCH), 3.81 (s, 3H, OCH3), 3.28 (dd, J = 14.2, 4.0 Hz, 1H,
CHH), 3.17 (dd, J = 14.2, 8.4 Hz, 1H, CHH), 2.10 (s, 3H, CH3);
13C NMR (75 MHz, CDCl3): δ 169.6, 159.2, 136.9, 134.1, 132.1,
129.5, 129.1, 127.1, 126.9, 125.4, 114.4, 71.3, 55.2, 40.8, 20.8;
HRMS (ESI-TOF): MNa+, found: 359.0483 (100); error = 1 ppm,
361.0457 (36); error = 1 ppm. requires C17H17ClNaO3S 359.0485,
361.0455.
4.2.31. 1-(3-Chlorophenyl)-2-((4-fluorophenyl)thio)ethyl acetate
(3id). m-Chlorostyrene (1i) (69 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3id (69
mg, 51%); light yellow viscous oil; Rf (10% EtOAc/hexanes)
0.40; IR (neat): νmax 1742, 1228 cm-1; 1H NMR (300 MHz, CDCl3):
δ 7.43–7.33 (m, 2H, ArH), 7.31–7.20 (m, 3H, ArH), 7.20–7.13
(m, 1H, ArH), 6.99 (br t, J = 8.7 Hz, 2H ArH), 5.79 (dd, J = 7.8,
5.5 Hz, 1H, ArCH), 3.31 (dd, J = 14.0, 7.8 Hz, 1H, CHH), 3.14 (dd,
J = 14.0, 5.5 Hz, 1H, CHH), 2.04 (s, 3H, CH3); 13C NMR (75 MHz,
CDCl3): δ 169.8, 162.1 (d, J = 246.1 Hz), 140.8, 134.5, 133.4 (d,
J = 8.1 Hz), 130.0 (d, J = 3.4 Hz), 129.8, 128.6, 126.7, 124.9,
116.1 (d, J = 21.8 Hz), 73.8, 41.2, 20.9; HRMS (ESI-TOF):
MNa+, found: 347.0281 (100); error = 1 ppm, 349.0256 (33);
error = 0.2 ppm. requires C16H14ClFNaO2S 347.0285, 349.0255.
4.2.27. 1-(4-Bromophenyl)-2-((4-fluorophenyl)thio)ethyl acetate
(3ad). p-Bromostyrene (1a) (91 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3ad (135
mg, 74%); colorless viscous oil; Rf (10% EtOAc/hexanes) 0.35;
1
IR (neat): νmax 1742, 1229 cm-1; H NMR (300 MHz, CDCl3): δ
7.45 (br d, J = 8.4 Hz, 2H, ArH), 7.40–7.33 (m, 2H, ArH), 7.17
(br d, J = 8.4 Hz, 2H, ArH), 6.99 (br t, J = 8.7 Hz, 2H, ArH),
5.79 (dd, J = 7.7, 5.8 Hz, 1H, ArCH), 3.32 (dd, J = 14.0, 7.7 Hz,
1H, CHH), 3.13 (dd, J = 14.0, 5.8 Hz, 1H, CHH), 2.03 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3): δ 169.8, 162.0 (d, J = 246.1
Hz), 137.7, 133.2(d, J = 8.1 Hz), 131.6, 130.0 (d, J = 3.3 Hz),
128.3, 122.4, 116.1 (d, J = 21.8 Hz), 73.8, 41.0, 20.9; HRMS
(ESI-TOF): MNa+, found: 390.9766 (92); error = 4 ppm,
392.9751 (100); error = 2 ppm. requires C16H14BrFNaO2S
390.9780, 392.9759.
4.2.32. 2-((4-Fluorophenyl)thio)-1-(3-formylphenyl)ethyl acetate
(3kd). m-Vinylbenzaldehyde (1k) (66 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3kd (74
mg, 59%); light yellow viscous oil; Rf (10% EtOAc/ hexanes)
1
0.33; IR (neat): νmax 1743, 1700, 1227 cm-1; H NMR (300 MHz,
CDCl3): δ 10.00 (s, 1H, CHO), 7.86–7.75 (m, 2H, ArH), 7.64–
7.44 (m, 2H, ArH), 7.43–7.28 (m, 2H, ArH), 6.99 (br t, J = 8.5
Hz, 2H, ArH), 5.91 (dd, J = 7.5, 5.8 Hz, 1H, ArCH), 3.38 (dd, J =
14.1, 7.5 Hz, 1H, CHH), 3.20 (dd, J = 14.1, 5.8 Hz, 1H, CHH), 2.06
(s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ 191.7, 169.8, 162.0
(d, J=246.2 Hz) 139.9, 136.5, 133.3 (d, J = 8.1 Hz), 132.7, 129.9,
129.2, 127.3, 116.1 (d, J = 21.8 Hz), 73.8, 41.0, 20.8; HRMS
(ESI-TOF): MNa+, found: 341.0615; error = 3 ppm. requires
C17H15FNaO3S 341.0624.
4.2.28. 1-(4-Chlorophenyl)-2-((4-fluorophenyl)thio)ethyl acetate
(3cd). p-Chlorostyrene (1c) (69 mg, 0.50 mmol). Column
chromatography (silica gel; 2% EtOAc/hexanes) yields 3cd (132
o
mg, 82%); white solid; mp = 41.0−42.0 C (EtOAc/hexanes); Rf
1
(10% EtOAc/hexanes) 0.43; IR (KBr): νmax 1743, 1239 cm-1; H
NMR (300 MHz, CDCl3): δ 7.42–7.25 (m, 6H, ArH), 7.02 (br t, J
= 8.6 Hz, 2H, ArH), 5.83 (dd, J = 7.7, 5.7 Hz, ArCH), 3.35 (dd, J

ACCEPTED MANUSCRIPT
8
Tetrahedron
4.2.33.
1-(2-Chlorophenyl)-2-((4-fluorophenyl)thio)ethyl
133.8 (A), 132.4 (A), 129.7 (B), 129.0 (A), 128.9 (B), 127.3 (A),
126.4 (B), 72.5 (B), 66.5 (A), 47.1 (A), 37.5 (B), 33.1 (A + B),
32.4 (A), 32.2 (B), 32.0 (B), 30.5 (A), 25.4 (A), 23.7 (B), 20.9
(B), 20.8 (A); HRMS (ESI-TOF): MNa+, found: 353.0188 (97);
error = 0.2 ppm, 355.0166 (100); error = 0 ppm. requires
C14H19BrNaO2S 353.0187, 355.0166.
acetate (3md). o-Chlorostyrene (1m) (70 mg, 0.50 mmol).
Column chromatography (silica gel; 2% EtOAc/hexanes) yields
3md (99 mg, 61%); colorless viscous oil; Rf
(10%
EtOAc/hexanes) 0.45; IR (neat): νmax 1747, 1227 cm-1; H NMR
(300 MHz, CDCl3): δ 7.45–7.41 (m, 3H, ArH), 7.34–7.22 (m,
3H, ArH), 7.00 (br t, J = 7.4 Hz, 2H, ArH), 6.28 (dd, J = 8.1, 4.3
Hz, 1H, ArCH), 3.31 (dd, J = 14.1, 4.3 Hz, 1H, CHH), 3.21 (dd, J =
14.1, 8.1 Hz, 1H, CHH), 2.08 (s, 3H, CH3); 13C NMR (75 MHz,
CDCl3): δ 169.6, 162.1 (d, J = 245.8), 136.6, 133.6 (d, J = 8.1
Hz,), 132,1, 130.2 (d, J = 3.3 Hz), 129.6, 129.3, 127.2, 127.0,
116.0 (d, J = 21.8 Hz), 71.2, 40.2, 20.8; HRMS (ESI-TOF):
MNa+, found: 347.0288 (100); error = 1 ppm, 349.0255 (30);
error = 0 ppm. requires C16H14ClFNaO2S 347.0285, 349.0255.
1
4.3.3. 3-Phenoxy-2-(phenylthio)propyl acetate (7ca) and 1-
phenoxy-3-(phenylthio)propan-2-yl acetate (7'ca) (3.7:1). Allyl
phenyl ether (6c) (67 mg, 0.50 mmol). Column chromatography
(silica gel; 2–5% EtOAc/hexanes) yields a mixture of 7ca (A)
and 7'ca (B) (73 mg, 48%, A:B = 3.7:1); colorless viscous oil; Rf
(10% EtOAc/hexanes) 0.32; IR (neat): νmax 1742, 1235 cm-1; 1H
NMR (400 MHz, CDCl3): δ 7.49 (d, J = 7.7 Hz, 2H of A, ArH),
7.41 (d, J = 8.0 Hz, 2H of B, ArH), 7.35–7.22 (m, 9H of A + B,
ArH), 7.18 (t, J = 7.3 Hz, 1H of B, ArH), 6.96 (t, J = 7.3 Hz, 2H
of A + B, ArH), 6.87 (br d, J = 8.2 Hz, 4H of A + B, ArH), 5.31–
5.24 (m, 1H of B, AcOCH), 4.41 (d, J = 6.0 Hz, 2H of A,
AcOCH2), 4.20–4.11 (m, 4H of A + B, ArOCH2), 3.70–3.62 (m, 1H
of A, ArSCH), 3.36–3.23 (m, 2H of B, ArSCH2), 2.04 (s, 3H of A,
CH3), 1.99 (s, 3H of B, CH3); 13C NMR (100 MHz, CDCl3): δ
170.7 (A), 170.3 (B), 158.3 (A), 158.2 (B), 135.2 (B), 133.3 (A),
132.4 (A), 129.7 (B), 129.5 (A + B), 129.1 (A), 129.0 (B), 127.7
(A), 126.5 (B), 121.2 (A + B), 114.5 (A + B), 71.2 (B), 67.1 (A +
B), 63.6 (A), 46.6 (A), 34.0 (B), 20.9 (B), 20.7 (A); HRMS (ESI-
TOF): MNa+, found: 325.0875; error = 0.3 ppm. requires
C17H18NaO3S 325.0874.
4.3. Synthesis of 1,2-acetoxysulfide derived from aliphatic alkenes
DIB (0.6 mmol, 193 mg), ArSSAr (0.3 mmol) and KI (0.5
mmol, 83 mg) were added to a solution of alkene substrate in
ClCH2CH2Cl (0.5 mmol in 2 mL of ClCH2CH2Cl), and the
suspension mixture was vigorously stirred at refluxing
temperature for 2 h. Upon completion, the reaction mixture was
cool down to room temperature and 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), brine (20 mL), dried
(anhydrous MgSO4), filtered, and concentrated (aspirator). The
residue was purified by column chromatography (SiO2) to furnish
analytically pure mixture of two regioisomeric products.
4.3.4. 3-(Benzyloxy)-2-(phenylthio)propyl acetate (7da) and 1-
(benzyloxy)-3-(phenylthio)propan-2-yl acetate (7'da) (3.7:1). p-
Allylbenzyl ether (6d) (74 mg, 0.50 mmol). Column
4.3.1. 2-(Phenylthio)octyl acetate (7aa) and 1-(phenylthio)octan-
2-yl acetate (7'aa) (1.9:1). 1-Octene (6a) (56 mg, 0.50 mmol).
Column chromatography (silica gel; 1% EtOAc/hexanes) yields a
mixture of 7aa (A) and 7'aa (B) (92 mg, 66%, A:B = 1.9:1);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.53; IR (neat): νmax
chromatography (silica gel; hexanes–5% EtOAc/hexanes) yields
a mixture of 7da (A) and 7'da (B) (102 mg, 65%. 3.7:1);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.26; IR (neat):
1
νmax 1741, 1237 cm-1; H NMR (300 MHz, CDCl3): δ 7.48–7.16
(m, 20H of A + B, ArH), 5.20–5.13 (m, 1H of B, AcOCH), 4.55
(s, 2 x 2H of A + B, ArCH2), 4.42–4.30 (m, 2H of A, AcOCH2),
3.75–3.63 (m, 4H of A + B, -OCH2), 3.60–3.51 (m, 1H of A,
ArSCH), 3.27 (dd, J = 14.0, 6.4 Hz, 1H of B, ArSCHH), 3.20 (dd,
J = 14.0, 6.3 Hz, 1H of B, ArSCHH), 2.02 (s, 2 x 3H of A + B,
CH3); 13C NMR (75 MHz, CDCl3): δ 170.7 (A), 170.4 (B), 137.8
(A), 137.7 (B), 135.6 (B), 133.8 (A), 131.9 (A), 129.6 (B), 129.0
(A), 128.9 (B), 128.4 (A + B), 127.7 (A + B), 127.64 (A), 127.62
(B), 127.3 (A), 126.4 (B), 73.24 (B), 73.17 (A), 71.7 (B), 69.4 (B),
69.2 A, 63.8 (A), 47.0 (A), 34.1 (B), 20.9 (B), 20.7 (A); HRMS
(ESI-TOF): MNa+, found: 339.1031; error = 0 ppm. requires
C18H20NaO3S 339.1031.
1
1743, 1236 cm-1; H NMR (300 MHz, CDCl3): δ 7.38–7.27 (m,
4H of A + B, ArH), 7.25–7.06 (m, 6H of A + B, ArH), 4.96–4.88
(m, 1H of B, AcOCH), 4.10 (dd, J = 11.3, 5.8 Hz, 1H of A,
AcOCHH), 4.01 (dd, J = 11.3, 7.2 Hz, 1H of A, AcOCHH), 3.26–
3.14 (m, 1H of A, ArSCH), 3.04 (dd, J = 13.8, 6.3 Hz, 1H of B,
ArSCHH), 2.96 (dd, J = 13.8, 5.8 Hz, 1H of B, ArSCHH), 1.91 (s,
3H of A, CH3), 1.87 (s, 3H of B, CH3), 1.69–1.31 (m, 8H of A +
B, CH2), 1.30–1.12 (m, 12H of A + B, CH2), 0.84–0.75 (m, 6H of
A + B, CH3); 13C NMR (75 MHz, CDCl3): δ 170.7 (A), 170.5
(B), 135.9 (B), 134.3 (A), 132.1 (A), 129.6 (B), 128.8 (A + B),
127.0 (A), 126.2 (B), 72.9 (B), 66.6 (A), 47.2 (A), 37.6 (B) 33.0
(B), 31.5 (A + B), 31.3 (A), 29.0 (A), 28.9 (B), 26.6 (A), 25.0 (B),
22.5 (A), 22.4 (B), 20.9 (B), 20.7 (A), 13.98 (A), 13.96 (B); HRMS
(ESI-TOF): MNa+, found: 303.1398; error = 1 ppm. requires
C16H24NaO2S 303.1395.
4.3.5. 3-(4-Methoxyphenyl)-2-(phenylthio)propyl acetate (7ea) and
1-(4-methoxyphenyl)-3-(phenylthio)propan-2-yl acetate (7'ea) (2.4:1).
p-Allylanisole (6e) (75 mg, 0.50 mmol). Column chromatography
(silica gel; hexanes–5% EtOAc/hexanes) yields a mixture of 7ea
(A) and 7'ea (B) (107 mg, 67%, A:B = 2.4:1) as colorless
viscous oil; Rf (10% EtOAc/hexanes) 0.26; IR (neat): νmax 1741,
4.3.2. 6-Bromo-2-(phenylthio)hexyl acetate (7ba) and 6-bromo-
1-(phenylthio)hexan-2-yl acetate (7'ba) (1.9:1). 6-Bromo-1-
hexene (6b) (81 mg, 0.50 mmol). Column chromatography (silica
gel; hexanes–5% EtOAc/hexanes) yields a mixture of 7ba (A)
and 7'ba (B) (92 mg, 58%, A:B = 1.9:1); light yellow viscous oil;
1
1247 cm-1; H NMR (300 MHz, CDCl3): δ 7.35–6.98 (m, 14H of
A + B, ArH), 6.80–6.70 (m, 4H of A + B, ArH), 5.12–5.03 (m,
1H of B, AcOCH), 4.11–3.99 (m, 2H of A, AcOCH2), 3.70 (s, 3H of
A, OCH3) 3.69 (s, 3H of B, OCH3), 3.50–3.39 (m, 1H of A,
ArSCH), 3.00–2.72 (m, 6H, ArCH2 of A + B and ArSCH2 of B),
2.04 (s, 3H of A, CH3), 1.93 (s, 3H of B, CH3); 13C NMR (75 MHz,
CDCl3): δ 170.7 (A), 170.3 (B), 158.3 (A + B), 135.7 (B), 134.1
(A), 132.2 (A), 130.4 (B), 130.14 (A), 130.06 (A), 129.5 (B),
128.92 (A), 128.89 (B), 128.6 (B), 127.2 (A), 126.2 (B), 113.8 (A
+ B), 73.6 (B), 65.6 (A), 55.2 (A + B), 48.7 (A), 38.1 (B), 37.0
(A), 36.4 (B), 20.9 (B), 20.7 (A); HRMS (ESI-TOF): MNa+,
found: 339.1030; error = 0.2 ppm. requires C18H20NaO3S
339.1031.
1
Rf (10% EtOAc/hexanes) 0.26; IR (neat): 1743, 1226 cm-1; H
NMR (300 MHz, CDCl3): δ 7.47–7.36 (m, 4H of A + B, ArH),
7.34–7.15 (m, 6H of A + B, ArH), 5.04–4.96 (m, 1H of B,
AcOCH), 4.20 (dd, J = 11.3, 5.6 Hz, 1H of A, AcOCHH), 4.08
(dd, J = 11.3, 7.4 Hz, 1H of A, AcOCHH), 3.45–3.35 (m, 4H of A
+ B, CH2Br), 3.37–3.20 (m, 1H of A, ArSCH), 3.14 (dd, J = 13.9,
6.1 Hz, 1H of B, ArSCHH), 3.03 (dd, J = 13.9, 6.0 Hz, 1H of B,
ArSCHH), 2.33–2.29 (m, 6H of A + B, CH2), 2.01 (s, 3H, CH3 of
A), 1.97 (s, 3H, CH3 of B), 1.94–1.37 (m, 12H of A + B, CH2);
13C NMR (75 MHz, CDCl3): δ 170.8 (A), 170.6 (B), 135.7 (B),

ACCEPTED MANUSCRIPT
9
4.3.6. 2-(Phenylthio)cyclohexyl acetate (7fa).12 Cyclohexene (6f)
(41 mg, 0.50 mmol). Column chromatography (silica gel; 1%
EtOAc/hexanes) yields 7fa (85 mg, 70%); colorless viscous oil;
Rf (10% EtOAc/hexanes) 0.41; IR (neat): νmax 1737, 1238 cm-1; 1H
NMR (300 MHz, CDCl3): δ 7.48–7.42 (m, 2H, ArH), 7.33–7.20 (m,
3H, ArH), 4.86–4.76 (m, 1H, AcOCH), 3.22–3.11 (m, 1H, ArSCH),
2.18–2.02 (m, 2H, CH2), 1.93 (s, 3H, CH3), 1.78–1.64 (m, 2H, CH2),
1.53–1.24, (m, 4H, CH2); 13C NMR (75 MHz, CDCl3): δ 170.3,
134.5, 132.2, 128.7, 126.8, 75.1, 50.1, 31.5, 31.2 , 24.9, 23.4, 20.9;
HRMS (ESI-TOF): MNa+, found: 273.0918; error = 3 ppm.
requires C14H18NaO2S 273.0925.
4.3.10. 2-((4-Methoxyphenyl)thio)octyl acetate (7ac) and 1-((4-
methoxyphenyl)thio)octan-2-yl acetate (7'ac) (2.0:1). 1-Octene
(6a) (57 mg, 0.51 mmol). Column chromatography (silica gel;
hexanes–5%EtOAc/hexanes) yields a mixture of 7ac (A) and
7'ac (B) (114 mg, 73%, A:B = 2.0:1); colorless viscous oil; Rf
(10% EtOAc/hexanes) 0.26; IR (neat): νmax 1741, 1247 cm-1; H
1
NMR (400 MHz, CDCl3): δ 7.37–7.24 (m, 4H of A + B, ArH),
6.76 (br d, J = 8.8 Hz, 4H of A + B, ArH), 4.91–4.83 (m, 1H of
B, AcOCH), 4.05 (dd, J = 11.2, 5.8, 1H of A, AcOCHH), 3.98 (dd, J
= 11.2, 5.8 Hz, 1H of A, AcOCHH), 3.71 (s, 3H of A, OCH3), 3.70
(s, 3H of B, OCH3), 3.03–2.95 (m, 1H of A, ArSCH), 2.95-2.83 (m,
2H of B, ArSCH2), 1.93 (s, 3H of A, CH3), 1.90 (s, 3H of B, CH3),
1.64–1.48 (m, 4H of A + B, CH2), 1.41–1.30 (m, 2H of A + B, CH2),
1.29–1.10 (m, 14H of A + B, CH2), 0.85–0.72 (m, 6H of A + B,
CH3); 13C NMR (100 MHz, CDCl3): δ 170.9 (A), 170.6 (B),
159.7 (A), 159.1 (B), 135.9 (A), 133.5 (B), 132.5 (B), 126.1 of A,
123.9 (B), 114.6 (B), 114.5 (A), 73.0(B), 66.6 (A), 55.3 (A and
B), 48.5 (A), 39.8 (B), 33.1 (B), 31.7 (A), 31.6 (B), 31.3 (A),
29.1 (A), 29.0 (B), 26.7 (A), 25.1 (B), 22.6 (A), 22.5 (B), 21.1
(B), 20.9 (A), 14.1 (A), 14.0 (B); HRMS (ESI-TOF): MNa+,
found: 333.1496; error = 1 ppm. requires C17H26NaO3S 333.1500.
4.3.7. 2-(p-Tolylthio)octyl acetate (7ab) and 1-(p-tolylthio)octan-2-yl
acetate (7'ab) (2.4:1). 1-Octene (6a) (56 mg, 0.50 mmol). Column
chromatography (silica gel; 1% EtOAc/hexanes) yields
a
mixture of 7ab (A) and 7'ab (B) (105 mg, 71%, A:B = 2.4:1);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.46; IR (neat):
νmax 2858, 1743, 1235 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.35–
7.26 (m, 4H of A + B, ArH), 7.10 (br d, J = 7.9 Hz, 4H of A + B,
ArH), 5.02–4.91 (m, 1H of B, AcOCH), 4.15 (dd, J = 11.3, 5.7
Hz, 1H of A, AcOCHH), 4.06 (dd, J = 11.3, 7.2 Hz, 1H of A,
AcOCHH), 3.23–3.13 (m, 1H of A, ArSCH), 3.07 (dd, J = 13.8,
6.3 Hz, 1H of B, ArSCHH), 2.99 (dd, J = 13.8, 5.7 Hz, 1H of B,
ArSCHH), 2.32 (s, 3H of A, ArCH3), 2.31 (s, 3H of B, ArCH3),
2.01 (s, 3H of A, CH3), 1.96 (s, 3H of B, CH3), 1.71–1.44 (m, 8H
of A + B, CH2), 1.39–1.20 (m, 12H of A + B, CH2), 0.94–0.82
(m, 6H of A + B, CH3); 13C NMR (75 MHz, CDCl3): δ 170.8 (A),
170.6 (B), 137.4 (A), 136.4 (B), 133.0 (A), 132.1 (B), 130.5 (B),
130.2 (A), 129.6 (A + B), 72.9 (B), 66.6 (A), 47.7 (A), 38.4 (B),
33.0 (B), 31.6 (A + B), 31.3 (A), 29.02 (A), 29.00 (B), 26.6 (A),
25.0 (B), 22.53 (A), 22.48 (B), 21.0 (A), 20.93 (B), 20.95 (B),
20.8 (A), 14.01 (A), 13.98 (B); HRMS (ESI-TOF): MNa+, found:
317.1552; error = 0 ppm. requires C17H26NaO2S 317.1552.
4.3.11. 3-(4-Methoxyphenyl)-2-((4-methoxyphenyl)thio)propyl acetate
(7ec) and 1-(4-methoxyphenyl)-3-(phenylthio)propan-2-yl acetate
(7'ec) (3.4:1). p-Allylanisole (6e) (74 mg, 0.50 mmol). Column
chromatography (silica gel; hexanes–5% EtOAc/hexanes) yields a
mixture of 7ec (A) and 7'ec (B) (107 mg, 62%, A:B = 3.4:1);
colorless viscous oil; Rf (20% EtOAc/hexanes) 0.35; IR (neat):
νmax 1739, 1246 cm-1; H NMR (300 MHz, CDCl3): δ 7.39–7.32
1
(m, 4H of A + B, ArH), 7.16–7.07 (m, 4H of A + B, ArH), 6.86–
6.79 (m, 8H of A + B, ArH), 5.16–5.07 (m, 1H of B, AcOCH),
4.10 (d, J = 6.0 Hz, 2H of A, AcOCH2), 3.78 (s, 4 x 3H of A + B,
OCH3), 3.39–3.28 (m, 1H of A, ArSCH), 3.00–2.76 (m, 6H,
ArCH2 of A + B and ArSCH2 of B), 2.03 (s, 3H of A, CH3), 1.92
(s, 3H of B, CH3); 13C NMR (75 MHz, CDCl3): δ 170.7 (A), 170.2
(B), 159.6 (A), 159.0 (B), 158.22 (B), 158.19 (A), 135.7 (A),
133.3 (B), 130.3 (B), 130.2 (A), 130.1 (A) 128.7 (B), 125.8 (B),
123.7 (A), 114.5 (B), 114.4 (A), 113.7 (A + B), 73.5 (B), 65.4
(A), 55.2 (A + B), 55.10 (A), 55.08 (B), 49.8 (A), 38.5 (B), 38.0
(B), 36.9 (A), 20.9 (B), 20.7 (A); HRMS (ESI-TOF): MNa+,
found: 369.1145; error = 2 ppm. requires C19H22NaO4S 369.1136.
4.3.8. 3-(4-Methoxyphenyl)-2-(p-tolylthio)propyl acetate (7eb) and
1-(4-methoxyphenyl)-3-(p-tolylthio)propan-2-yl
acetate
(7'eb)
(2.2:1). p-Allylanisole (6e) (75 mg, 0.50 mmol). Column
chromatography (silica gel; hexanes–5% EtOAc/hexanes) yields
a mixture of 7eb (A) and 7'eb (B) (127 mg, 80%, A:B = 2.2:1);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.26; IR (neat):
νmax 1741, 1245 cm-1; 1H NMR (300 MHz, CDCl3, ): δ 7.24–7.14
(m, 4H of A + B, ArH), 7.06–6.95 (m, 8H of A + B, ArH), 6.73
(br t, J = 8.5 Hz, 4H of A + B, ArH) 5.08–4.99 (m, 1H of B,
AcOCH), 4.08–3.94 (m, 2H of A, AcOCH2), 3.68 (s, 3H of A,
OCH3), 3.66 (s, 3H of B, OCH3), 3.41–3.29 (m, 1H of A, ArSCH),
2.95–2.68 (m, 6H, ArCH2 of A + B and ArSCH2 of B), 2.22 (s, 3H
of A, ArCH3), 2.21 (s, 3H of B, ArCH3), 1.92 (s, 3H of A, CH3),
1.82 (s, 3H of B, CH3); 13C NMR (75 MHz, CDCl3): δ 170.7 (A),
170.2 (B), 158.3 (B), 158.2 (A), 137.5 (A), 136.4 (B), 133.0 (A),
131.9 (B), 130.4 (B), 130.3 (B), 130.09 (A), 130.06 (A), 129.7
(A), 129.6 (A + B), 128.6 (B), 113.7 (A + B), 73.5 (B), 65.4 (A),
55.09 (A), 55.07 (B), 49.1 (A), 38.0 (B), 37.2 (B), 37.0 (A), 21.0
(A), 20.9 (B), 20.8 (B), 20.7 (A); HRMS (ESI-TOF): MNa+,
found: 353.1199; error = 3 ppm. requires C19H22NaO3S 353.1187.
4.3.12. 2-((4-Methoxyphenyl)thio)cyclohexyl acetate (7fc).
Cyclohexene (6f) (41 mg, 0.50 mmol). Column chromatography
(silica gel; 1% EtOAc/hexanes) yields 7fc (103 mg, 73%);
colorless viscous oil; Rf (20% EtOAc/ hexanes) 0.46; IR (neat):
νmax 1738, 1732, 1243 cm-1; H NMR (300 MHz, CDCl3): δ 7.37
1
(br d, J = 8.9 Hz, 2H, ArH), 6.81 (br d, J = 8.9 Hz, 2H, ArH),
4.75–4.62 (m, 1H, AcOCH), 3.76 (s, 3H, OCH3), 2.97–2.82 (m,
1H, ArSCH), 2.08–1.91 (m, 2H, CH2), 1.96 (s, 3H, CH3), 1.71–
1.51 (m, 2H, CH2), 1.40–1.14 (m, 4H, CH2); 13C NMR (75 MHz,
CDCl3): δ 170.3, 159.4, 135.9, 123.6, 114.2, 74.6, 55.1, 50.9,
31.5, 31.3, 24.9, 23.5, 21.1; HRMS (ESI-TOF): MNa+, found:
303.1020; error = 4 ppm. requires C15H20NaO3S 303.1031.
4.3.9. 2-(4-Tolylthio)cyclohexyl acetate (7fb). Cyclohexene (6f)
(43 mg, 0.52 mmol). Column chromatography (silica gel; 1%
EtOAc/hexanes) yields 7fb (74 mg, 56%); colorless viscous oil;
Rf (10% EtOAc/hexanes) 0.46; IR (neat): νmax 1736, 1238 cm-1;
1H NMR (300 MHz, CDCl3): δ 7.34 (br d, J = 8.0 Hz, 2H, ArH),
7.09 (br d, J = 8.0 Hz, 2H, ArH), 4.79–4.71 (m, 1H, AcOCH),
3.10–3.00 (m, 1H, ArSCH), 2.32 (s, 3H, ArCH3), 2.12–2.00 (m,
2H, CH2), 1.96 (s, 3H, CH3), 1.74–1.59 (m, 2H, CH2), 1.47–1.18
(m, 4H, CH2); 13C NMR (75 MHz, CDCl3): δ 170.3, 137.2, 133.1,
130.3, 129.5, 74.9, 50.5, 31.6, 31.2, 24.9, 23.4, 21.04, 21.00;
HRMS (ESI-TOF): MNa+, found: 287.1082; error = 0 ppm.
requires C15H20NaO2S 287.1082.
4.3.13 2-((4-Fluorophenyl)thio)octyl acetate (7ad) and 1-((4-
fluoro phenyl)thio)octan-2-yl acetate (7'ad) (1.7:1). 1-Octene
(6a) (57 mg, 0.51 mmol). Column chromatography (silica gel;
hexanes–5% EtOAc/hexanes) yields a mixture of 7ad (A) and
7'ad (B) (112 mg, 74%, A:B = 1.7:1); colorless viscous oil; Rf
1
(20% EtOAc/hexanes) 0.46; IR (neat): νmax 1743, 1231 cm-1; H
NMR (300 MHz, CDCl3): δ 7.46–7.35 (m, 4H of A + B, ArH),
7.02–6.94 (m, 4H of A + B, ArH), 4.98–4.90 (m, 1H of B,
AcOCH), 4.13 (dd, J = 11.3, 5.9 Hz, 1H of A, AcOCHH), 4.05 (dd,
J = 11.3, 7.0 Hz, 1H of A, AcOCHH), 3.19–3.10 (m, 1H of A,
ArSCH) 3.04 (dd, J = 13.9, 6.4 Hz, 1H of B, ArSCHH), 2.97 (dd, J
= 13.9, 5.6 Hz, 1H of B, ArSCHH), 2.00 (s, 3H of A, CH3), 1.96 (s,

ACCEPTED MANUSCRIPT
10
Tetrahedron
Cohen, J.; Perun, T. J.; Plattner, J. J. J. Med. Chem. 1987, 30,
1729–1737.
Conchillo, A.; Camps, F.; Messeguer, A. J. Org. Chem. 1990, 55,
1728–1735.
3H of B, CH3), 1.70–1.38 (m, 6H of A + B, CH2), 1.36–1.16
(m, 14H of A + B, CH2), 0.92–0.81 (m, 6H of A + B, CH3); 13C
NMR (75 MHz, CDCl3): 170.7 (A), 170.6 (B), 162.4 (d, J =
246.4 Hz, A), 161.9 (d, J = 245.3 Hz, B), 135.2 (d, J = 8.1 Hz,
A), 132.7 (d, J = 8.0 Hz, B), 130.8 (d, J = 3.3 Hz, B), 129.0 (d, J
= 3.4 Hz, A), 116.2 (d, J = 21.7 Hz, A + B), 72.8 (B), 66.5 (A)
48.2 (A), 39.0 (B) 33.0 (B), 31.6 (A + B), 31.2 (A), 29.0 (A), 28.9
(B), 26.6 (A), 25.0 (B), 22.51 (A), 22.46 (B), 20.9 (B), 20.7 (A),
13.99 (A), 13.96 (B); HRMS (ESI-TOF): MNa+, found:
321.1304; error = 1 ppm. requires C16H23FNaO3S 321.1300.
3.
4.
(a) Chong, J. M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 1560–
1563. (b) Vougioukas, A. E.; Kagan, H. B. Tetrahedron Lett.
1987, 28, 6065–6068. (c) Iqbal, J.; Pandey, A.; Shukla, A.;
Srivastaca, R. R.; Tripathi, S. Tetrahedron 1990, 46, 6423–6432.
(d) Chini, M.; Crotti, P.; Giovani, E.; Macchia, F.; Pineschi, M.
Synlett 1992, 303–305. (e) Tanabe, Y.; Mori, K.; Yoshida, Y. J.
Chem. Soc., Perkin Trans. 1 1997, 671–675. (f) Still, J. W. J.;
Martin, L. P. J. Synth. Commun. 1998, 28, 913–923. (g) Sasaki,
M.; Tanino, K.; Miyashita, M. J. Org. Chem. 2001, 66, 5388–
5394. (h) Fringuelli, F.; Pizzo, F.; Tortoioli, S.; Vaccaro, L. Adv.
Synth. Catal. 2002, 344, 379–384. (i) Fringuelli, F.; Pizzo, F.;
Tortoioli, S.; Vaccaro, L. Tetrahedron Lett. 2003, 44, 6785–6787.
(j) Amantini, D.; Fringuelli, F.; Pizzo, F.; Tortoioli, S.; Vaccaro,
L. Synlett 2003, 2292–2296. (k) Fringuelli, F.; Pizzo, F.; Tortoioli,
S.; Vaccaro, L. J. Org. Chem. 2003, 68, 8248–8251. (l) Fringuelli,
F.; Pizzo, F.; Tortoioli, S.; Vaccaro, L. Green Chem. 2003, 5,
436–440. (m) Fan, R.-H.; Hou, X.-L. J. Org. Chem. 2003, 68,
726–730. (n) Wu, J.; Xia, H.-G. Green Chem. 2005, 7, 708–710.
(o) Pironti, V.; Colonna, S. Green Chem. 2005, 7, 43–45. (p)
Chen, J.; Wu, H.; Jin, C.; Zhang, X.; Xie, Y.; Su, W. Green Chem.
2006, 8, 330–332. (q) Su, W.; Chen, J.; Wu, H.; Jin, C. J. Org.
Chem. 2007, 72, 4524–4527. (r) Gao, P.; Xu, P.-F.; Zhai, H.
Tetrahedron Lett. 2008, 49, 6536–6538. (s) Abaee, M. S.;
Mojtahedi, M. M.; Abbasi, H.; Fatemi, E. R. Synth. Commun.
2008, 38, 282–289.
4.3.14. 2-((4-Fluorophenyl)thio)-3-(4-methoxyphenyl)propyl acetate
(7ed) and 1-((4-fluorophenyl)thio)-3-(4-methoxy phenyl)propan-2-yl
acetate (7'ed) (2.1:1). p-Allylanisole (6e) (74 mg, 0.50 mmol).
Column chromatography (silica gel; hexanes–5% EtOAc
/hexanes) yields a mixture of 7ed (A) and 7'ed (B) (116 mg,
70%, A:B
=
2.1:1); colorless viscous oil; Rf
(10%
EtOAc/hexanes) 0.30; IR (neat): νmax 1741, 1247 cm-1; H NMR
(300 MHz, CDCl3): δ 7.42–7.31 (m, 4H A + B, ArH), 7.15–7.06
(m, 4H of A + B, ArH), 7.03–6.94 (m, 4H A + B, ArH), 6.88–
6.79 (m, 4H of A + B, ArH), 5.16–5.08 (m, 1H of B, AcOCH),
4.13–4.10 (m, 2H of A, AcOCH2), 3.78 (s, 3H of A, OCH3), 3.77 (s,
3H of B, CH3), 3.49–3.35 (m, 1H of A, ArSCH), 3.01–2.79 (m, 6H,
ArCH2 of A + B and ArSCH2 of B), 2.02 (s, 3H of A, CH3), 1.92 (s,
3H of B, CH3); 13C NMR (75 MHz, CDCl3): δ 170.6 (A) , 170.2
(B), 162.4 (d, J = 246.6 Hz, A), 161.8 (d, J = 254.4 Hz, B),
158.3 (A + B), 135.2 (A) (d, J = 8.1 Hz), 132.5 (d, J = 8.0 Hz,
B), 130.5 (d, J = 3.3 Hz, B), 130.3 (B), 130.1 (A), 129.9 (A),
128.9 (d, J = 3.3 Hz, A), 128.5 (B), 115.98 (d, J = 21.7 Hz, A),
115.95 (d, J = 21.7 Hz, B), 113.8 (A + B), 73.4 (B), 65.4 (A),
55.10 (A), 55.08 (B), 49.8 (A), 38.1 (B), 37.7 (B), 37.0 (A), 20.8
(B), 20.7 (A); HRMS (ESI-TOF): MNa+, found: 357.0941; error
= 1 ppm. requires C18H19FNaO3S 357.0937.
1
4.3.15. 2-((4-Fluorophenyl)thio)cyclohexyl acetate (7fd).
Cyclohexene (6f) (41 mg, 0.50 mmol). Column chromatography
(silica gel; 1% EtOAc/hexanes) yields 7fd (93 mg, 69%);
colorless viscous oil; Rf (10% EtOAc/hexanes) 0.46; IR (neat):
1
νmax 1738, 1238 cm-1; H NMR (300 MHz, CDCl3): δ 7.39–7.33
(m, 2H, ArH), 6.91 (br t, J = 8.7 Hz, 2H, ArH), 4.72–4.63 (m,
1H, AcOCH), 2.99–2.90 (m, 1H, ArSCH), 2.05–1.92 (m, 2H,
CH2), 1.89 (s, 3H, CH3), 1.71–1.58 (m, 2H, CH2), 1.39–1.12 (m,
4H, CH2); 13C NMR (75 MHz, CDCl3): δ 170.3, 162.3 (d, J =
246.2 Hz), 135.3 (d, J = 8.1 Hz), 128.9 (d, J = 3.4 Hz), 115.8 (d,
J = 21.6 Hz), 74.8, 50.8, 31.5, 31.3, 24.9, 23.5, 21.0; HRMS
(ESI-TOF): MNa+, found: 291.0831; error = 0 ppm. requires
C14H17FNaO2S 291.0831.
Acknowledgement
5.
6.
(a) Nakatsukasa, S.; Takai, K.; Utimoto, K. J. Org. Chem. 1986,
51, 5045–5046. (b) Hosomi, A.; Ogata, K.; Hoashi, K.; Kohra, S.;
Tominaga, Y. Chem. Pharm. Bull. 1988, 36, 3736–3738. (c)
Engstrom, G.; Morelli, M.; Palomo, C.; Mitzel, T. Tetrahedron
Lett. 1999, 40, 5967–5970. (d) Mitzel, T.; Palomo, C.; Jendza, K.
J. Org. Chem. 2002, 67, 136–145.
(a) Beckwith, A. L. J.; Wagner, R. D. J. Org. Chem. 1981, 46,
3638–3645. (b) Szmant, H. H.; Mata, A. J.; Namis, A. J.;
Panthananickal, A. M. Tetrahedron 1976, 32, 2665–2680.
Surendra, K.; Krishnaveni, N. S.; Sridhar, R.; Rao, K. R. J. Org.
Chem. 2006, 71, 5819–5821.
We thank the Thailand Research (TRF; DBG5480017),
Center of Excellence for Innovation in Chemistry (PERCH-CIC),
and Mahidol University under the National Research Universities
Initiative and the Development and Promotion of Science and
Technology Talent Project (DPST), the Institute for the
Promotion of Teaching Science and Technology for financial
supports.
7.
8.
9.
References and notes
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13. Yadav, L. D. S.; Awasthi, C. Tetrahedron Lett. 2009, 50, 3801–
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14. Katrun, P.; Chiampanichayakul, S.; Korworapan, K.; Pohmakotr,
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1
15. The H NMR data of our synthesized compounds 3ba and 3ea are
in good agreement with those previously reported by Taniguchi,
1
N. (Ref. 12). Thus, H NMR assignments of new acetoxysulfides
derived from other styrene derivatives reported in this work are on
the basis of those of 3ba and 3ea.
16. Compound 7' (minor isomer, B) possesses methine proton signal
adjacent to the acetoxy group at δ ≈ 5 ppm while compound 7
(major isomer, A) possesses methylene proton signal adjacent to
the acetoxy group at
δ ≈ 4 ppm. Assignments of other
acetoxysulfides (mixture of two regioisomers) derived from
aliphatic alkenes are on the same basis.
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D.-F.; Yu, J.-Q. Org. Lett. 2006, 8, 3387–3390.
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