A route to benzylic arylsulfoxides from β-ketosulfoxides

Article abstract of DOI:10.1016/j.tet.2016.05.038

The K₂CO₃-mediated benzylation of β-ketosulfoxides 4 with 2.0?equiv of benzylic halides 5 affords benzylic arylsulfoxides 6 in moderate yields along with trace amounts of chalcones 7. The products 6 are assumed to form in situ intermediates of sulfenate anions from β-ketosulfoxides which are commonly involved in carbon–sulfur bond formation. A plausible mechanism has been proposed.

Full text of DOI:10.1016/j.tet.2016.05.038

Accepted Manuscript
A route to benzylic arylsulfoxides from β-ketosulfoxides
Meng-Yang Chang, Yu-Chieh Cheng, Chieh-Kai Chan
PII:
S0040-4020(16)30423-9
10.1016/j.tet.2016.05.038
TET 27765
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 April 2016
Revised Date: 10 May 2016
Accepted Date: 13 May 2016
Please cite this article as: Chang M-Y, Cheng Y-C, Chan C-K, A route to benzylic arylsulfoxides from β-
ketosulfoxides, Tetrahedron (2016), doi: 10.1016/j.tet.2016.05.038.
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A Route to Benzylic Arylsulfoxides from β-Ketosulfoxides
Meng-Yang Chang,* Yu-Chieh Cheng and Chieh-Kai Chan
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan
O
O
O
S
O
S
K CO
Y
2
3
Y
2
+
+
Ar
Y
Ar
R
R
acetone
X
5
7
4
6

ACCEPTED MANUSCRIPT
Tetrahedron
1
TETRAHEDRON
Pergamon
A Route to Benzylic Arylsulfoxides from β-Ketosulfoxides
Meng-Yang Chang,* Yu-Chieh Cheng and Chieh-Kai Chan
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan
Abstract—The K2CO3-mediated benzylation of β-ketosulfoxides 4 with 2.0 equivalents of benzylic halides 5 affords
benzylic arylsulfoxides 6 in moderate yields along with trace amounts of chalcones 7. The products 6 are assumed to form in
situ intermediates of sulfenate anions from β-ketosulfoxides which are commonly involved in carbon-sulfur bond formation.
A plausible mechanism has been proposed.
Despite a number of successful reports on the synthetic
1. Introduction
applications of 1, it is still significant to find new
precursors with a high level of chemical control. Due to the
importance of such intermediates, the development of a
new precursor of 1 with a broad substrate scope is still
highly desirable. Herein, we introduce β-ketosulfoxides 4
as a synthon of 1 and demonstrate its ability in the
conversion of benzylic halide into benzylic arylsulfoxide.
Pioneering works by the groups of Perrio, Poli, Walsh and
Schwan have been developed to access difunctionalized
sulfoxides via one-pot alterative strategies (Scheme 2).12
Generally, sulfoxides are generated by the metal complexes
catalyzed oxidation of sulfides with oxidants13 or the
nucleophilic substitution of sulfinates with organometallic
reagents.14 As part of our ongoing efforts toward α-
substituted β-ketosulfones,15 the α-benzylation of β-
ketosulfoxides is examined.
Sulfenate anion (1), a conjugated base of a sulfenic acid,
is known to act as a highly reactive species in the
1 -2
synthetic
and biological arenas.3 From palladium-
catalyzed, base-promoted or fluoride-mediated carbon-
sulfur bond cleavage and formation processes, this
intermediate sulfenate anion has been generated and
trapped in situ from diversified precursors, including 2-
carbons chain of β-sulfinyl esters 2a,4-5 β-sulfinyl silanes
2b,6 and 2-sulfinyl acrylates 2c;7 3-carbon chains of allyl
aryl sulfoxides 3a;8 and 1-carbon chains of aryl benzyl
sulfoxides 3b9 and benzyl t-butyl sulfoxides 3c.10 The
complementary routes based on the release of sulfenate
anions have became viable alternatives for the enantio- and
diastereoselective syntheses of substituted sulfoxides.4a,11
General synthetic routes to sulfenate anion (1) are
summarized in Scheme 1.
Scheme 2. Applications of sulfenate anion precursors
4c
5b
Perrio
E
Poli
Scheme 1. Synthetic routes to sulfenate anions (1)
Pd(II)
KOH
O
O
S
O
S
O
S
NaHMDS
S
Ph
(eq 1)
(eq 3)
(eq 5)
(eq 2)
1
Ar
Ar
Ar
E
Ar
Ar
Ar
Ar
OH
1
Ph
Ar
Br
X
Ar
O
O
S
O
S
S
R
Me
Me
6c-d
7a
Ar
R
sulfenic acid
R
Walsh
TMS
Schwan
Pd(II)
CsF
O
S
O
S
O
O
4
Me
3c, R = Ar
CySLi
H-B
B
ref 10
S
Ph
S
(eq 4)
(eq 6)
this work
1
Ar
E
Ar
1
Ar
X
Ph
Br
O
S
O
O
S
O
S
Ar
S
8
9a
9d
E
R
R
Poli
Walsh / Schwan
O
refs 4-5
ref 9
ref 8
R
R
Pd(II)
base
O
S
O
2a, E = ester
3b, R = Ar
sulfenate anion (1)
t-BuOK
1
S
Ar
S
Ar
1
1
Ar
Ar
Ar
Ar
Ar
Ar
1
1
X
Ar
ref 6
R
X
Ar
(2.5 mol%)
O
S
O
S
ref 7
10b
Perrio
O
This work
O
R
TMS
O
S
Pd(II)
base
O
S
O
O
S
2b
3a, R = Ar
base
1
1
E
R
S
Me
Ar
S
(eq 7)
(eq 8)
1
Ar
Ar
R
R
Ar
1
2c
X
Ar
Ar
X 5
Me Me
4
6
2. Results and discussion
———
Keywords: Sulfenate anion; β-Ketosulfoxides; Benzylic halides.
*Corresponding author. Tel.: +886 7 3121101 ext 2220
e-mail: mychang@kmu.edu.tw
To demonstrate the conversion from 4 to 6, we employed
coupling materials, 4a and 5c, as the model substrates to

ACCEPTED MANUSCRIPT
2
Tetrahedron
Table 2. Synthesis of 6a
investigate the reaction conditions. Initially, the use of
various bases (Cs2CO3, K2CO3, NaH, t-BuOK) was
investigated, as shown in Table 1. Entries 1-2 show that
poorer yields of 6c are observed in the presence of Cs2CO3
and K2CO3 (2.0 equiv) in refluxing THF for 5 h. Among
these bases screened, NaH and t-BuOK provides an
unknown mixture (entries 3-4). After changing the solvents
from THF to acetone, the yield of 6c was enhanced slightly.
In entries 5-6, K2CO3 produced a higher yield (30%) than
Cs2CO3 (18%). While controlling K2CO3 as the base, the
factors of time and equivalents were studied next. When the
time was elongated to 20 h, the yield was improved to 50%.
However, after an additional 5 h, the yield was decreased to
44% (entries 7-8). By increasing the equivalents of K2CO3
(2.0 ꢀ 3.3), 6c was provided in 70% yield, as shown in
entry 9. With excess amounts of K2CO3 (5.0 equiv), a
lower yield (61%) was observed (entry 10). When the
solvent was changed to warm DMF, no desired 6c was
isolated. Among entries 1-11, we hypothesized that low
conversion to 7c is due to the Michael reaction of chalcone
with acetone. By elevating the temperature, elongating the
time and increasing the base equivalents, more amounts of
the complex mixture were derived from 7c. These results
show that 3.3 equivalents of K2CO3 caused a competition
between the debenozylative benzylation of the sulfenate
anion (for 6c) and the benzylative desulfenylation of 4a
(for 7c). In particular, 4a auto-decomposed in the absence
of 5c in acetone at reflux for 80 h (entry 12). Overall, we
believe that the system consisting of K2CO3 (3.3
equiv)/boiling acetone/20 h is an optimal combination for
generating 6c.
O
O
S
O
S
K CO
3
Y
2
Y
2
+
Ar
R
R
acetone
X
5
4
6
entry 4, Ar =, R =
5, Y =, X =
5a, Ph, Br
6 (%)b
6a, 76
6b, 70
6c, 70
6d, 68
6e, 70
6f, 73
1
2
3
4
5
6
7
8
9
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
4a, Ph, Ph
5b, 2-FC6H4, Br
5c, 3-MeOC6H4, Br
5d, 4-FC6H4, Br
5e, 4-NO2C6H4, Br
5f, 4-PhC6H4 , Br
5g, 1-naphthalene, Br 6g, 72
5h, 2-quinoline, Br
5i, 9-anthracene, Br
5j, CH=CH2, Br
5a, Ph, Br
6h, 65
6i, 60
6j, 65
6k, 70
6l, 72
6m, 73
6n, 67
10 4a, Ph, Ph
11 4b, Ph, 3-MeOC6H4
12 4b, Ph, 3-MeOC6H4
13 4b, Ph, 3-MeOC6H4
14 4b, Ph, 3-MeOC6H4
15 4b, Ph, 3-MeOC6H4
16 4b, Ph, 3-MeOC6H4
17 4c, Ph, 4-FC6H4
18 4c, Ph, 4-FC6H4
19 4c, Ph, 4-FC6H4
20 4c, Ph, 4-FC6H4
21 4c, Ph, 4-FC6H4
22 4d, Ph, PhCH2
5b, 2-FC6H4, Br
5c, 3-MeOC6H4, Br
5e, 4-NO2C6H4, Br
5g, 1-naphthalene, Br 6o, 65
5h, 2-quinoline, Br
5a, Ph, Br
6p, 60
6q, 68
6r, 64
6s, 67
6t, 63
5b, 2-FC6H4, Br
5c, 3-MeOC6H4, Br
5e, 4-NO2C6H4, Br
5g, 1-naphthalene, Br 6u, 60
Table 1. Optimization conditionsa
5a, Ph, Br
6v, 76
6w, 78
6x, 77
23 4d, Ph, PhCH2
5b, 2-FC6H4, Br
5c, 3-MeOC6H4, Br
O
O
O
S
conditions
OMe
O
S
24 4d, Ph, PhCH2
Ph
+
Ph
+
Ph
Ph
OMe
MeO
25 4d, Ph, PhCH2
5g, 1-naphthalene, Br 6y, 76
Br
6c
7c
4a
5c
26 4e, 4-MeOC6H4, Ph
27 4f, 4-NO2C6H4, Ph
28 4g, 4-PhC6H4, Ph
5a, Ph, Br
5a, Ph, Br
5a, Ph, Br
6a, 71
6a, 70
6a, 73
6a, 71
6a, 68
6a, 66
6b, 70
6b, 62
6c, 62
6c, 69
temp time
(oC) (h)
yield (%)b
6c
entry base (equiv) /solvent
7c
c
1
2
3
4
5
6
7
8
9
Cs2CO3 (2.0) / THF
K2CO3 (2.0) / THF
NaH (2.0) / THF
67
67
67
67
57
57
57
57
57
25
100
57
5
5
10
─
29 4h, 3,4-CH2O2C6H3, Ph 5a, Ph, Br
c
<5
─
30 4i, 2-naphthalene, Ph
31 4j, 3,4-Cl2C6H3, Ph
32 4e, 4-MeOC6H4, Ph
33 4f, 4-NO2C6H4, Ph
34 4e, 4-MeOC6H4, Ph
35 4f, 4-NO2C6H4, Ph
36 4a, Ph, Ph
5a, Ph, Br
d
d
5
─
5a, Ph, Br
t-BuOK (2.0) / THF
Cs2CO3 (2.0) / acetone
K2CO3 (2.0) / acetone
K2CO3 (2.0) / acetone
K2CO3 (2.0) / acetone
K2CO3 (3.3) / acetone
5
─
5b, 2-FC6H4, Br
5b, 2-FC6H4, Br
5c, 2-MeOC6H4, Br
5c, 2-MeOC6H4, Br
c
5
18
30
50
44
70
61
─
5
8
20
25
20
25
5
20
12
5k, (E)-CH=CHPh, Cl 6z, 70
c
─
37 4a, Ph, Ph
5l, 2-pyridine, Cl
5m, 3,4-(MeO)2-2-
pyridine, Cl
5n, 3,5-Me2-4-MeO-2-
pyridine, Cl
6aa, 65
6ab, 60
10 K2CO3 (5.0) / acetone
11 K2CO3 (3.3) / DMF
12 K2CO3 (5.0) / acetone
10
38 4a, Ph, Ph
d
e
─
80
─
39 4a, Ph, Ph
40 4a, Ph, Ph
6ac, 60
aThe reaction was run on 4a (1.0 mmol), 5c (2.0 equiv),
solvents (10 mL). bIsolated yields. cNo detection. dComplex
products. eRemoval of 5c.
5o, 2-benzothiazole, Cl 6ad, 55
aThe reaction was run on 4 (1.0 mmol), 5 (2.0 mmol), K2CO3
(3.3 mmol), acetone (10 mL), 57 oC, 20 h. bIsolated yields.

ACCEPTED MANUSCRIPT
Tetrahedron
3
The proposed mechanism is illustrated in Scheme 3.
Beginning with 4a, the K2CO3-mediated α-benzylation of
4a with 5c generates A. Through the thermal-assisted
intramolecular [2,3]-sigmatropic rearrangement of A (for β-
H), B is formed along with chalcones 7c. Following the
deprotonation of B by K2CO3, in situ formed 1 undergoes
nucleophilic substitution with 5c to provide 6c. Through
the involvement of acetone, only minor amounts of 7c were
yielded.
(R = Ph, 3-MeOC6H4, 4-FC6H4, PhCH2) to 8a-d was
performed with a yield range of 15~31%, as shown in
Scheme 5. Compared with the given yields of 6a-ad, 8a-d
were produced in lower yields. Based on the above results,
we envision that the sulfenate anion was not easily released
via the alkylation of 4a-d with secondary 5p followed by a
sequential [2,3]-sigmatropic rearrangement. Compounds
8a-d were generated as two inseparated diastereoisomers
with two chiral centers at carbon and sulfur atoms.
Interestingly, 8d, generated from the benzyl sulfenate anion,
provided a ratio of 8:1. Attempts to use a tertiary trityl
chloride (5q) failed to produce 8e due to steric hindrance
inhibiting the alkylation procedure. To change the aryl
group (4a-j) to the methyl group (4k), 6a was isolated in a
42% yield.
Scheme 3. Proposed mechanism
O
O
S
O
Y
Ph
S
O
K CO
3
Y
2
α
+
Ph
Ph
Ph
O
Ph
acetone
Br
5c
H
β
Y
= 3-MeOC
H
H
Y
6
4
4a
A
7c
O
Ph
S
Scheme 5. Synthesis of 8a-d and 6a
K CO
2
3
Y
Br
O
O
H
Ph
Ph
S
5
K CO
2
3
Y
S
S
B
Ph
O
O
S
O
S
O
O
K CO
3
complex
mixture
Me
Ph
2
Ph
2
6c
+
Ph
R
R
acetone
Br
5p
Me
8a, R = Ph (21%)
8b, R = 3-MeOC H (31%)
4a-d
With the optimized conditions for the K2CO3-mediated
reaction of 4a and 5c in boiling acetone, the substrate scope
of β-ketosulfoxides 4a-j (Ar = Ph, 4-MeOC6H4, 4-NO2C6H4,
4-PhC6H4, 3,4-CH2O2C6H3, 2-naphthalene, 3,4-Cl2C6H3; R
= Ph, 3-MeOC6H4, 4-FC6H4, CH2Ph) and aryl halides 5a-o
(Y = Ph, 2-FC6H4, 3-MeOC6H4, 4-FC6H4, 4-NO2C6H4, 4-
PhC6H4, 1-naphthalene, 2-quinoxline, 9-anthracene, vinyl,
cinnamyl, 2-pyridine, 3,4-(MeO)2-2-pyridine, 3,5-Me2-4-
MeO-2-pyridine, 2-benzothiazole; X = Br, Cl) was
investigated, as shown in Table 2. In this process, a variety
of benzylic arylsulfoxides 6a-ad could be prepared from
the reaction of 4 with 2.0 equivalents of benzylic halides 5
in the presence of 3.3 equivalents of K2CO3 with a range of
50%~78% yield. For the Ar and R substituents of 4, the
diversified electron-withdrawing or electron-donating aryl
groups were well tolerated. When the Y group of 5 was
tricyclic anthracene 5i, heterocyclic quinoline 5h, pyridine
5l-n and benzothiazole 5o, the desired skeleton 6 was
formed. For the X group (Br and Cl) of 5, no obvious yield
changes were observed. The structure of 6f was determined
by single-crystal X-ray crystallography.16
6
4
8c, R = 4-FC H (15%)
6
4
8d, R = CH Ph (22%)
2
Ph
O
O
O
S
O
K CO
3
Ph
2
Ph
Ph
Ph
S
2
+
+
Ph
Me
Ph
Ph
Ph
acetone
Cl
Ph
5q
4a
4k
8e (not detected)
O
3
O
S
K CO
2
Ph
Ph
S
2
Ph
acetone
Br
5a
6a (42%)
Scheme 6. Control experiments
O
S
5a
(1 equiv)
Ph
Ph
O
O
S
6a (38%)
Br
Br
K CO
2
3
(eq 1)
+
+
Ph
Ph
NO
O N
2
2
acetone
O
4a
(1 equiv)
S
5e
(1 equiv)
6e (20%)
O
S
5a
(1 equiv)
Ph
Ph
O
O
S
Scheme 4. Structures of 6ac and omeprazole
6a (30%)
K CO
Br
2
3
(eq 2)
+
Ph
+
Ph
acetone
O
4a
(1 equiv)
OMe
OMe
S
5l
Me
Me
Me
Me
N
N
H
N
O
O
(1 equiv)
6aa (35%)
Cl
S
S
N
N
N
O
O
S
omeprazole
OMe
6ac
Ph
K CO
2
4a
(0.5 equiv)
3
O
S
(eq 3)
+
In Scheme 4, 6ac, a stable surrogate of omeprazole, was
synthesized by the one-pot route.17a Omeprazole is reported
as a proton pump inhibitor used to treat gastroesophageal
reflux disease and stomach ulcers.17-18 Moreover, when 2.0
g of 4a (8.2 mmol) was treated with the combination, 1.02
g of 6a was isolated in a 58% yield. This route can be
enlarged to a gram scale. Changing the primary bromide 5a
to a secondary bromide 5p, the one-pot conversion of 4a-d
acetone
Ph
O
O
S
Br
5a
6a (49%)
Ph
(2 equiv)
4f
(0.5 equiv)
O N
2
To extend the limitation of this one-pot domino route for
cross coupling (Scheme 6), the reaction of 4a with 5a and
5e was examined first. In Eq. 1, 6a and 6e were provided in

ACCEPTED MANUSCRIPT
4
Tetrahedron
38% and 20% yields, respectively. Compound 4a should
prefer to alkylate 5e with better reactivity such that the
resulting sulfonate anion could trap 5a to generate 6a in a
higher yield. We believe that the reactivity is a key factor
affecting the product distribution. Compared with 5a (X =
Br) and 5l (X = Cl), similar yields of 6a (30%) and 6aa
(33%) were obtained by involving different leaving groups,
as shown in Eq. 2. Furthermore, treatment of 4a (Ar = Ph)
and 4f (Ar = 4-NO2C6H4) with 5a provided 6a in 49% yield
via the exchange of the intermolecular aryl group (Eq. 3).
The control experiments could explain the plausible
mechanism.
was added the resulting crude product in CH2Cl2 (10 mL)
o
o
at 0 C. The reaction mixture was stirred at 25 C for 30
min. NaHCO3 (1 g) was added to the stirred solution at 25
o
oC. The reaction mixture was stirred at 25 C for 20 min.
Then, water (10 mL) was added to the stirred solution at 25
o
oC. The reaction mixture was stirred at 25 C for 20 min.
The reaction mixture was extracted with CH2Cl2 (3 x 20
mL). The combined organic layers were washed with brine,
dried, filtered and evaporated to afford crude product under
reduced
pressure.
Purification
on
silica
gel
(hexanes/EtOAc = 4/1~1/1) afforded 4.
4.2.1. 2-Benzenesulfinyl-1-phenylethanone (4a). Yield =
70% (171 mg); Colorless solid; mp = 70-82 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
3. Conclusion
1
M++1) calcd for C14H13O2S 245.0636, found 245.0639; H
In summary, we developed a novel route for preparing
various benzylic arylsulfoxides 6 in moderate yields via
K2CO3-mediated benzylation of β-ketosulfoxides 4 with 2.0
equivalents of benzylic halides 5. A plausible mechanism
was proposed for the synthesis of 6 by the in situ-generated
sulfonate anion. The structure of the key product was
confirmed by X-ray crystallography. Further investigations
regarding the synthetic application of β-ketosulfoxides will
be conducted and published.
NMR (400 MHz, CDCl3): δ 7.88-7.85 (m, 2H), 7.71-7.66
(m, 2H), 7.59-7.55 (m, 1H), 7.50-7.41 (m, 5H), 4.56 (d, J =
14.0 Hz, 1H), 4.29 (d, J = 14.0 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 191.30, 143.22, 135.92, 134.09, 131.52,
129.28 (2x), 128.73 (2x), 128.71 (2x), 124.20 (2x), 65.95.
4.2.2. 2-(3-Methoxybenzenesulfinyl)-1-phenylethanone
(4b). Yield = 73% (200 mg); Colorless gum; HRMS (ESI,
1
M++1) calcd for C15H15O3S 275.0742, found 275.0748; H
NMR (400 MHz, CDCl3): δ 7.88-7.86 (m, 2H), 7.60-7.56
(m, 1H), 7.46-7.42 (m, 2H), 7.37 (t, J = 8.0 Hz, 1H), 7.26-
7.25 (m, 1H), 7.19 (dt, J = 0.4, 6.8 Hz, 1H), 6.99 (ddd, J =
0.8, 2.8, 8.0 Hz, 1H), 4.55 (d, J = 14.0 Hz, 1H), 4.28 (d, J
= 14.0 Hz, 1H), 3.81 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 191.25, 160.37, 144.66, 135.96, 134.09, 130.26, 128.74
(2x), 128.72 (2x), 118.06, 116.21, 108.43, 66.06, 55.50.
4. Experimental section
4.1. General. All other reagents and solvents were
obtained from commercial sources and used without
further purification. Reactions were routinely carried out
under an atmosphere of dry nitrogen with magnetic stirring.
Products in organic solvents were dried with anhydrous
magnesium sulfate before concentration in vacuo. Melting
points were determined with a SMP3 melting apparatus. 1H
and 13C NMR spectra were recorded on a Varian INOVA-
400 spectrometer operating at 400/200 and at 100 MHz,
respectively. Chemical shifts (δ) are reported in parts per
million (ppm) and the coupling constants (J) are given in
Hertz. High resolution mass spectra (HRMS) were
measured with a mass spectrometer Finnigan/Thermo
Quest MAT 95XL. X-ray crystal structures were obtained
with an Enraf-Nonius FR-590 diffractometer (CAD4,
Kappa CCD). Elemental analyses were carried out with
Heraeus Vario III-NCSH, Heraeus CHN-OS-Rapid
Analyzer or Elementar Vario EL III.
4.2.3.
2-(4-Fluorobenzenesulfinyl)-1-phenylethanone
(4c). Yield = 75% (197 mg); Colorless gum; HRMS (ESI,
M++1) calcd for C14H12FO2S 263.0542, found 263.0545;
1H NMR (400 MHz, CDCl3): δ 7.81-7.78 (m, 2H), 7.66-
7.61 (m, 2H), 7.54-7.50 (m, 1H), 7.39-7.35 (m, 2H), 7.13-
7.08 (m, 2H), 4.51 (d, J = 14.4 Hz, 1H), 4.29 (d, J = 14.4
Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 191.16, 164.23 (d,
J = 250.9 Hz), 138.42 (d, J = 3.1 Hz), 135.57, 133.99,
128.57 (2x), 128.46 (2x), 126.50 (d, J = 9.1 Hz, 2x),
116.37 (d, J = 22.8 Hz, 2x), 65.66; Anal. Calcd for
C14H11FO2S: C, 64.11; H, 4.23. Found: C, 64.32; H, 4.45.
4.2.4. 1-Phenyl-2-phenylmethanesulfinylethanone (4d).
o
Yield = 73% (188 mg); Colorless solid; mp = 127-129 C
(recrystallized from hexanes and EtOAc); HRMS (ESI,
4.2. A representative synthetic procedure of skeleton 4
is as follows: K2CO3 (304 mg, 2.2 mmol) was added to a
solution of thiophenol (1.0 mmol) in acetone (10 mL) at 25
oC. The reaction mixture was stirred at 25 oC for 10 min. α-
Bromoketone (1.0 mmol) was added to the reaction
mixture at 25 oC. The reaction mixture was stirred at 25 oC
for 8 h. The reaction mixture was concentrated. The
residue was diluted with water (10 mL) and the mixture
was extracted with CH2Cl2 (3 x 20 mL). The combined
organic layers were washed with brine, dried, filtered and
evaporated to afford crude product under reduced pressure.
Without further purification, freshly prepared m-
chloroperoxybenzoic acid (mCPBA, 170 mg, 1.0 mmol)
1
M++1) calcd for C15H15O2S 259.0793, found 259.0795; H
NMR (400 MHz, CDCl3): δ 7.91-7.88 (m, 2H), 7.63-7.59
(m, 1H), 7.50-7.45 (m, 2H), 7.37-7.30 (m, 5H), 4.28 (d, J =
13.2 Hz, 1H), 4.23 (d, J = 15.2 Hz, 1H), 4.12 (d, J = 15.2
Hz, 1H), 4.11 (d, J = 13.2 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 192.54, 135.89, 134.26, 130.38 (2x), 129.09,
128.84 (2x), 128.83 (2x), 128.59 (2x), 128.51, 57.66, 57.56.
4.2.5. 2-Benzenesulfinyl-1-(4-methoxyphenyl)ethanone
(4e). Yield = 75% (206 mg); Colorless solid; mp = 86-88
oC (recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C15H15O3S 275.0742, found 275.0749; H
NMR (400 MHz, CDCl3): δ 7.78 (d, J = 8.8 Hz, 2H), 7.63-

ACCEPTED MANUSCRIPT
Tetrahedron
5
7.60 (m, 2H), 7.43-7.40 (m, 3H), 6.82 (d, J = 8.8 Hz, 2H),
13C NMR (100 MHz, CDCl3): δ 189.27, 142.64, 138.81,
4.45 (d, J = 14.4 Hz, 1H), 4.19 (d, J = 14.4 Hz, 1H), 3.77
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 189.41, 164.05,
143.08, 131.22, 130.98 (2x), 129.03 (2x), 128.80, 123.97
(2x), 113.72 (2x), 65.55, 55.30.
135.59, 133.47, 131.73, 130.82, 130.59, 129.38 (2x),
127.85, 124.07 (2x), 65.19; Anal. Calcd for C14H10Cl2O2S:
C, 53.69; H, 3.22. Found: C, 53.81; H, 3.17.
4.2.11. 1-Benzenesulfinylpropan-2-one (4k).19 Yield =
70% (127 mg); Colorless solid; mp = 60-61 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
4.2.6. 2-Benzenesulfinyl-1-(4-nitrophenyl)ethanone (4f).
o
Yield = 76% (220 mg); Colorless solid; mp = 90-91 C
1
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C14H12NO4S 290.0487, found 290.0485;
1H NMR (400 MHz, CDCl3): δ 8.25-8.21 (m, 2H), 8.04-
8.00 (m, 2H), 7.64-7.60 (m, 2H), 7.50-7.46 (m, 3H), 4.50
(d, J = 14.4 Hz, 1H), 4.38 (d, J = 14.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ 190.17, 150.46, 142.34, 140.30,
131.72, 129.84 (2x), 129.35 (2x), 123.97 (2x), 123.73 (2x),
65.18.
M++1) calcd for C9H11O2S 183.0480, found 183.0488; H
NMR (200 MHz, CDCl3): δ 7.69-7.56 (m, 5H), 3.86-3.75
(m, 2H), 2.25 (s, 1H).
4.3. A representative synthetic procedure of skeleton 6
is as follows: K2CO3 (460 mg, 3.3 mmol) was added to a
o
solution of 4 (1.0 mmol) in acetone (10 mL) at 25 C. The
o
reaction mixture was stirred at 25 C for 10 min. Benzylic
halide 5 (2.0 mmol) was added to the reaction mixture at
o
o
25 C. The reaction mixture was stirred at 57 C for 20 h.
4.2.7. 2-Benzenesulfinyl-1-biphenyl-4-ylethanone (4g).
o
o
Yield = 77% (246 mg); Colorless solid; mp = 99-100 C
The reaction mixture was cooled to 25 C and the solvent
(recrystallized from hexanes and EtOAc); HRMS (ESI,
was concentrated. The residue was diluted with water (10
mL) and the mixture was extracted with CH2Cl2 (3 x 20
mL). The combined organic layers were washed with brine,
dried, filtered and evaporated to afford crude product under
1
M++1) calcd for C20H17O2S 321.0949, found 321.0951; H
NMR (400 MHz, CDCl3): δ 7.93 (d, J = 8.4 Hz, 2H), 7.72-
7.69 (m, 2H), 7.63 (d, J = 8.4 Hz, 2H), 7.59-7.56 (m, 2H),
7.51-7.37 (m, 6H), 4.57 (d, J = 14.0 Hz, 1H), 4.32 (d, J =
14.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 190.76,
146.53, 143.12, 139.18, 134.51, 131.41, 129.26 (2x),
129.19 (2x), 128.84 (2x), 128.37, 127.17 (2x), 127.08 (2x),
124.10 (2x), 65.80.
reduced
pressure.
Purification
on
silica
gel
(hexanes/EtOAc = 2/1~1/2) afforded 6.
4.3.1. 1-Benzenesulfinylmethylbenzene (6a). For 4a,
yield = 76% (164 mg); For 4k, yield = 42% (91 mg);
o
Colorless solid; mp = 129-131 C (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
4.2.8.
2-Benzenesulfinyl-1-benzo[1,3]dioxol-5-yl-
1
ethanone (4h). Yield = 76% (219 mg); Colorless gum;
C13H13OS 217.0687, found 217.0689; H NMR (400 MHz,
HRMS (ESI, M++1) calcd for C15H13O4S 289.0535, found
CDCl3): δ 7.47-7.36 (m, 5H), 7.29-7.22 (m, 3H), 6.98-6.96
(m, 2H), 4.08 (d, J = 12.8 Hz, 1H), 3.99 (d, J = 12.4 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 142.67, 131.06,
130.26 (2x), 129.75 (2x), 129.00, 128.34 (2x), 128.14,
124.34 (2x), 63.52.
1
289.0542; H NMR (400 MHz, CDCl3): δ 7.66-7.63 (m,
2H), 7.49-7.46 (m, 3H), 7.43 (dd, J = 2.0, 8.4 Hz, 1H),
7.31 (d, J = 2.0 Hz, 1H), 6.78 (d, J = 8.4 Hz, 1H), 6.01 (s,
2H), 4.45 (d, J = 14.4 Hz, 1H), 4.18 (d, J = 14.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 189.08, 152.66, 148.28,
143.18, 131.42, 130.81, 129.19 (2x), 125.87, 124.11 (2x),
107.90, 107.87, 102.02, 65.77; Anal. Calcd for C15H12O4S:
C, 62.49; H, 4.20. Found: C, 62.67; H, 4.41.
4.3.2. 1-Benzenesulfinylmethyl-2-fluorobenzene (6b).
o
Yield = 70% (164 mg); Colorless solid; mp = 89-91 C
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C13H12FOS 235.0593, found 235.0598; 1H
NMR (400 MHz, CDCl3): δ 7.41-7.32 (m, 5H), 7.22-7.16
(m, 1H), 7.01-6.95 (m, 2H), 6.91-6.86 (m, 1H), 4.05 (d, J =
12.8 Hz, 1H), 4.00 (d, J = 12.4 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 160.80 (d, J = 246.4 Hz), 142.46, 132.16
(d, J = 3.0 Hz), 131.00, 129.96 (d, J = 7.5 Hz), 128.59 (2x),
123.93 (2x), 123.77 (d, J = 3.8 Hz), 116.62 (d, J = 15.2
Hz), 114.96 (d, J = 22.0 Hz), 56.20.
4.2.9.
2-Benzenesulfinyl-1-naphthalen-2-yl-ethanone
(4i). Yield = 75% (221 mg); Colorless solid; mp = 96-97
oC (recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C18H15O2S 295.0793, found 295.0796; H
NMR (400 MHz, CDCl3): δ 8.26 (s, 1H), 7.84-7.79 (m,
2H), 7.73-7.64 (m, 4H), 7.52-7.37 (m, 5H), 4.61 (d, J =
14.4 Hz, 1H), 4.37 (d, J = 14.4 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 190.94, 142.95, 135.42, 132.91, 131.79,
131.16, 131.00, 129.40, 128.96 (2x), 128.79, 128.31,
127.40, 126.68, 123.91 (2x), 123.16, 65.65; Anal. Calcd
for C18H14O2S: C, 73.44; H, 4.79. Found: C, 73.62; H, 4.95.
4.3.3. 1-Benzenesulfinylmethyl-3-methoxybenzene (6c).
Yield = 70% (172 mg); Colorless gum; HRMS (ESI, M++1)
1
calcd for C14H15O2S 247.0793, found 247.0796; H NMR
(400 MHz, CDCl3): δ 7.37-7.32 (m, 5H), 7.07 (t, J = 8.0
Hz, 1H), 6.73 (dd, J = 2.4, 8.0 Hz, 1H), 6.53 (d, J = 7.6 Hz,
1H), 6.41 (t, J = 2.0 Hz, 1H), 3.97 (d, J = 12.4 Hz, 1H),
3.87 (d, J = 12.4 Hz, 1H), 3.58 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 159.07, 142.44, 130.77, 130.20, 129.03,
128.48 (2x), 124.02 (2x), 122.29, 114.99, 113.86, 63.19,
54.71.
4.2.10.
2-Benzenesulfinyl-1-(3,4-
dichlorophenyl)ethanone (4j). Yield = 70% (218 mg);
Colorless solid; mp = 84-87 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C14H11Cl2O2S 312.9857, found 312.9855; H NMR (400
MHz, CDCl3): δ 7.90 (d, J = 2.0 Hz, 1H), 7.69 (dd, J = 2.0,
8.0 Hz, 1H), 7.66-7.63 (m, 2H), 7.52 (s, 1H), 7.51-7.48 (m,
3H), 4.43 (d, J = 14.0 Hz, 1H), 4.26 (d, J = 14.0 Hz, 1H);

ACCEPTED MANUSCRIPT
6
Tetrahedron
Hz, 1H), 4.34 (d, J = 12.4 Hz, 1H), 4.27 (d, J = 12.0 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 150.97, 147.57,
142.81, 136.34, 130.92, 129.53, 128.73 (2x), 128.60,
127.29, 126.89, 126.48, 123.86 (2x), 122.35, 65.75.
4.3.4. 1-Benzenesulfinylmethyl-4-fluorobenzene (6d).
Yield = 68% (159 mg); Colorless solid; mp = 149-150 C
o
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C13H12FOS 235.0593, found 235.0599; 1H
NMR (400 MHz, CDCl3): δ 7.39-7.29 (m, 5H), 6.87 (br s,
2H), 6.85 (br s, 2H), 3.96 (d, J = 12.8 Hz, 1H), 3.91 (d, J =
12.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 162.46 (d, J
= 245.6 Hz), 142.16, 131.80 (d, J = 8.4 Hz, 2x), 130.97,
128.65 (2x), 124.59 (d, J = 3.0 Hz), 124.07 (2x), 115.06 (d,
J = 21.9 Hz, 2x), 61.85; Anal. Calcd for C13H11FOS: C,
66.64; H, 4.73. Found: C, 66.82; H, 4.79.
4.3.9. 9-Benzenesulfinylmethylanthracene (6i). Yield =
60% (190 mg); Colorless solid; mp = 138-139 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C21H17OS 317.1000, found 317.1008; H
NMR (400 MHz, CDCl3): δ 8.44 (s, 1H), 8.01-7.97 (m,
4H), 7.45-7.39 (m, 4H), 7.33-7.28 (m, 1H), 7.21-7.16 (m,
4H), 5.33 (d, J = 13.2 Hz, 1H), 4.99 (d, J = 13.2 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 131.17 (2x), 131.09 (2x),
131.06, 129.06 (2x), 128.65 (3x), 126.45 (2x), 125.03 (3x),
124.12 (2x), 123.66 (2x), 120.91, 57.47.
4.3.5. 1-Benzenesulfinylmethyl-4-nitrobenzene (6e).
o
Yield = 70% (183 mg); Colorless solid; mp = 163-165 C
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C13H12NO3S 262.0538, found 262.0541;
1H NMR (400 MHz, CDCl3): δ 8.04 (d, J = 8.8 Hz, 2H),
7.48-7.39 (m, 3H), 7.34-7.31 (m, 2H), 7.07 (d, J = 8.4 Hz,
2H), 4.18 (d, J = 12.8 Hz, 1H), 3.98 (d, J = 12.8 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 147.56, 141.62, 136.11,
131.44, 131.12 (2x), 129.00 (2x), 124.00 (2x), 123.13 (2x),
61.60.
4.3.10. (Prop-2-ene-1-sulfinyl)benzene (6j). Yield = 65%
(108 mg); Colorless oil; HRMS (ESI, M++1) calcd for
1
C9H11OS 167.0531, found 167.0533; H NMR (400 MHz,
CDCl3): δ 7.57-7.54 (m, 2H), 7.50-7.45 (m, 3H), 5.66-5.55
(m, 1H), 5.29 (dq, J = 1.2, 10.8 Hz, 1H), 5.16 (dq, J = 1.2,
16.8 Hz, 1H), 3.53 (dd, J = 7.6, 12.8 Hz, 1H), 3.47 (dd, J =
7.6, 12.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 142.70,
130.98, 128.90 (2x), 125.07, 124.20 (2x), 123.75, 60.66.
4.3.6. 4-Benzenesulfinylmethylbiphenyl (6f). Yield =
73% (213 mg); Colorless solid; mp = 198-199 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
4.3.11. (3-Methoxybenzenesulfinylmethyl)benzene (6k).
Yield = 70% (172 mg); Colorless gum; HRMS (ESI, M++1)
1
M++1) calcd for C19H17OS 293.1000, found 293.1005; H
1
calcd for C14H15O2S 247.0793, found 247.0798; H NMR
NMR (400 MHz, CDCl3): δ 7.58-7.55 (m, 2H), 7.50-7.42
(m, 9H), 7.38-7.33 (m, 1H), 7.06 (d, J = 8.4 Hz, 2H), 4.12
(d, J = 12.8 Hz, 1H), 4.06 (d, J = 12.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ 142.75, 141.03, 140.34, 131.16,
130.75 (2x), 128.86 (2x), 128.77 (2x), 128.03, 127.47,
127.05 (2x), 126.99 (2x), 124.41 (2x), 63.23; Anal. Calcd
for C19H16OS: C, 78.05; H, 5.52. Found: C, 78.16; H, 5.75.
X-Ray diagram: crystal of compound 6f was grown by
slow diffusion of EtOAc into a solution of compound 6f in
CH2Cl2 to yield colorless prisms. The compound
crystallizes in the orthorhombic crystal system, space
group P c a 21, a = 8.1512(5) Å, b = 5.4945(4) Å, c =
32.278(2) Å, V = 1445.65(17) Å3, Z = 4, dcalcd= 1.274
g/cm3, F(000) = 556, 2θ range 1.262~26.409o, R indices
(all data) R1 = 0.0402, wR2 = 0.1172.
(400 MHz, CDCl3): δ 7.19-7.11 (m, 4H), 6.90-6.79 (m,
5H), 3.93 (d, J = 12.8 Hz, 1H), 3.89 (d, J = 12.4 Hz, 1H),
3.57 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 159.52,
143.58, 129.94 (2x), 129.30, 128.68, 127.90 (2x), 127.71,
117.42, 115.93, 108.04, 62.81, 54.92.
4.3.12.
1-Fluoro-2-(3-
methoxybenzenesulfinylmethyl)benzene (6l). Yield =
72% (190 mg); Colorless gum; HRMS (ESI, M++1) calcd
1
for C14H14FO2S 265.0699, found 265.0695; H NMR (400
MHz, CDCl3): δ 7.18-7.09 (m, 2H), 6.95-6.88 (m, 2H),
6.85-6.80 (m, 4H), 3.94 (s, 2H), 3.56 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 160.63 (d, J = 247.1 Hz), 159.54,
143.69, 132.01 (d, J = 3.0 Hz), 129.73 (d, J = 8.3 Hz),
129.34, 123.53 (d, J = 3.8 Hz), 117.48, 116.47 (d, J = 15.2
Hz), 115.81, 114.72 (d, J = 21.2 Hz), 107.78, 55.93, 54.87.
4.3.7. 1-Benzenesulfinylmethylnaphthalene (6g). Yield =
72% (192 mg); Colorless gum; HRMS (ESI, M++1) calcd
4.3.13.
1-Methoxy-3-(3-
1
methoxybenzenesulfinylmethyl)benzene (6m). Yield =
for C17H15OS 267.0844, found 267.0843; H NMR (400
73% (201 mg); Colorless gum; HRMS (ESI, M++1) calcd
MHz, CDCl3): δ 7.98-7.54 (m, 1H), 7.84-7.82 (m, 1H),
7.78 (d, J = 8.4 Hz, 1H), 7.52-7.45 (m, 2H), 7.41-7.27 (m,
6H), 6.99 (d, J = 7.2 Hz, 1H), 4.67 (d, J = 12.8 Hz, 1H),
4.34 (d, J = 12.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
143.08, 133.42, 131.72, 131.02, 129.46, 129.00, 128.60
(2x), 128.56, 126.37, 125.77, 125.55, 124.96, 124.08 (2x),
123.17, 61.90.
1
for C15H17O3S 277.0899, found 277.0897; H NMR (400
MHz, CDCl3): δ 7.19-7.15 (m, 1H), 7.04-7.00 (m, 1H),
6.84-6.83 (m, 1H), 6.82 (br s, 2H), 6.68 (dd, J = 2.8, 8.4
Hz, 1H), 6.49 (d, J = 7.2 Hz, 1H), 6.80 (t, J = 1.6 Hz, 1H),
3.88 (d, J = 12.8 Hz, 1H), 3.82 (d, J = 12.8 Hz, 1H), 3.56
(s, 3H), 3.52 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
159.51, 158.92, 143.77, 130.15, 129.26, 128.84, 122.19,
117.25, 115.86, 114.90, 113.64, 108.03, 62.97, 54.86,
54.54.
4.3.8. 2-Benzenesulfinylmethylquinoline (6h). Yield =
65% (174 mg); Colorless gum; HRMS (ESI, M++1) calcd
1
for C16H14NOS 268.0796, found 268.0802; H NMR (400
4.3.14.
1-(3-Methoxybenzenesulfinylmethyl)-4-
MHz, CDCl3): δ 7.95 (d, J = 8.4 Hz, 1H), 7.92 (d, J = 8.4
Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.58 (dt, J = 1.6, 8.4 Hz,
1H), 7.47-7.39 (m, 3H), 7.35-7.28 (m, 3H), 7.15 (d, J = 8.4
nitrobenzene (6n). Yield = 67% (195 mg); Colorless solid;
mp = 114-116 oC (recrystallized from hexanes and EtOAc);

ACCEPTED MANUSCRIPT
Tetrahedron
7
HRMS (ESI, M++1) calcd for C14H14NO4S 292.0644,
found 292.0650; H NMR (400 MHz, CDCl3): δ 8.02 (d, J
Calcd for C13H10F2OS: C, 61.89; H, 4.00. Found: C, 61.96;
H, 4.12.
1
= 8.8 Hz, 2H), 7.28 (t, J = 8.0 Hz, 1H), 7.09 (d, J = 8.8 Hz,
2H), 6.92 (ddd, J = 0.8, 2.4, 8.0 Hz, 1H), 6.86-6.84 (m,
1H), 6.84 (br s, 1H), 4.16 (d, J = 12.8 Hz, 1H), 3.95 (d, J =
12.8 Hz, 1H), 3.67 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
160.01, 147.42, 143.00, 136.19, 131.07 (2x), 129.87,
123.01 (2x), 117.63, 115.90, 108.37, 61.53, 55.28.
4.3.19.
1-(4-Fluorobenzenesulfinylmethyl)-3-
methoxybenzene (6s). Yield = 67% (177 mg); Colorless
gum; HRMS (ESI, M++1) calcd for C14H14FO2S 265.0699,
1
found 265.0702; H NMR (400 MHz, CDCl3): δ 7.34-7.29
(m, 2H), 7.10 (d, J = 7.6 Hz, 1H), 7.07-7.02 (m, 2H), 6.77-
6.75 (m, 1H), 6.50 (d, J = 7.6 Hz, 1H), 6.45-6.44 (m, 1H),
4.01 (d, J = 12.4 Hz, 1H), 3.87 (d, J = 12.4 Hz, 1H), 3.63
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 164.10 (d, J =
250.2 Hz), 159.25, 137.94 (d, J = 3.0 Hz), 129.99, 129.23,
126.49 (d, J = 8.3 Hz, 2x), 122.37, 115.86 (d, J = 22.7 Hz,
2x), 115.24, 113.92, 63.36, 54.85; Anal. Calcd for
C14H13FO2S: C, 63.62; H, 4.96. Found: C, 63.75; H, 5.10.
4.3.15.
1-(3-
Methoxybenzenesulfinylmethyl)naphthalene (6o). Yield
= 65% (192 mg); Colorless gum; HRMS (ESI, M++1)
1
calcd for C18H17O2S 297.0949, found 297.0951; H NMR
(400 MHz, CDCl3): δ 7.87-7.84 (m, 1H), 7.73-7.70 (m,
1H), 7.68 (d, J = 8.4 Hz, 1H), 7.41-7.34 (m, 2H), 7.23-7.19
(m, 1H), 7.14-7.10 (m, 1H), 6.98 (d, J = 7.2 Hz, 1H), 6.84-
6.81 (m, 3H), 4.51 (d, J = 12.8 Hz, 1H), 4.27 (d, J = 12.8
Hz, 1H), 3.51 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
159.42, 144.21, 133.05, 131.43, 129.22, 129.17, 128.59,
128.16, 125.99, 125.42, 125.30, 124.63, 122.86, 117.34,
115.81, 107.82, 61.28, 54.76.
4.3.20.
1-(4-Fluorobenzenesulfinylmethyl)-4-
nitrobenzene (6t). Yield = 63% (176 mg); Colorless solid;
mp = 137-139 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++1) calcd for C13H11FNO3S 280.0444,
1
found 280.0446; H NMR (400 MHz, CDCl3): δ 8.07 (d, J
= 8.8 Hz, 2H), 7.35-7.30 (m, 2H), 7.15-7.08 (m, 4H), 4.18
(d, J = 12.8 Hz, 1H), 3.98 (d, J = 12.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ 164.42 (d, J = 250.9 Hz), 147.66,
137.08 (d, J = 3.0 Hz), 135.82, 131.16 (2x), 126.39 (d, J =
9.1 Hz, 2x), 123.26 (2x), 116.43 (d, J = 22.7 Hz, 2x), 61.73.
4.3.16. 2-(3-Methoxybenzenesulfinylmethyl)quinoline
(6p). Yield = 60% (178 mg); Colorless gum; HRMS (ESI,
M++1) calcd for C17H16NO2S 298.0902, found 298.0906;
1H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 8.4 Hz, 1H),
7.99 (d, J = 8.4 Hz, 1H), 7.77 (dd, J = 1.2, 8.0 Hz, 1H),
7.70-7.66 (m, 1H), 7.52-7.48 (m, 1H), 7.29 (t, J = 8.4 Hz,
1H), 7.25 (d, J = 8.4 Hz, 1H), 7.07-7.04 (m, 2H), 6.95-6.92
(m, 1H), 4.40 (d, J = 12.4 Hz, 1H), 4.33 (d, J = 12.4 Hz,
1H), 3.66 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 160.10,
151.24, 147.86, 144.55, 136.54, 129.89, 129.79, 128.88,
127.48, 127.17, 126.73, 122.64, 117.94, 116.21, 108.07,
66.15, 55.28.
4.3.21. 1-(4-Fluorobenzenesulfinylmethyl)naphthalene
(6u). Yield = 60% (170 mg); Colorless oil; HRMS (ESI,
M++1) calcd for C17H14FOS 285.0749, found 285.0754; 1H
NMR (400 MHz, CDCl3): δ 7.92-7.88 (m, 1H), 7.83-7.79
(m, 1H), 7.77 (d, J = 8.4 Hz, 1H), 7.49-7.44 (m, 2H), 7.29
(d, J = 8.4 Hz, 1H), 7.28-7.23 (m, 2H), 7.01-6.96 (m, 3H),
4.68 (d, J = 12.4 Hz, 1H), 4.28 (d, J = 12.4 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ 164.18 (d, J = 250.1 Hz),
138.33 (d, J = 3.1 Hz), 133.38, 131.64, 129.44, 129.06,
128.56, 126.41, 126.39 (d, J = 9.1 Hz, 2x), 125.82, 125.17,
124.92, 123.08, 115.81 (d, J = 26.7 Hz, 2x), 61.75.
4.3.17. (4-Fluorobenzenesulfinylmethyl)benzene (6q).
o
Yield = 68% (159 mg); Colorless solid; mp = 133-135 C
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C13H12FOS 235.0593, found 235.0599; 1H
NMR (400 MHz, CDCl3): δ 7.32-7.28 (m, 2H), 7.25-7.19
(m, 3H), 7.09-7.04 (m, 2H), 6.94-6.91 (m, 2H), 4.06 (d, J =
12.4 Hz, 1H), 3.95 (d, J = 12.4 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 164.21 (d, J = 250.2 Hz), 137.86 (d, J =
3.1 Hz), 130.18 (2x), 128.55, 128.32 (2x), 128.17, 126.56
(d, J = 8.3 Hz, 2x), 115.96 (d, J = 22.7 Hz, 2x), 63.30.
4.3.22. (Phenylmethanesulfinylmethyl)benzene (6v).
Yield = 76% (175 mg); Colorless solid; mp = 132-134 C
o
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C14H15OS 231.0844, found 231.0842; H
1
NMR (400 MHz, CDCl3): δ 7.36-7.28 (m, 6H), 7.27-7.24
(m, 4H), 3.89 (d, J = 12.8 Hz, 2H), 3.80 (d, J = 12.8 Hz,
2H); 13C NMR (100 MHz, CDCl3): δ 129.82 (2x), 129.75
(4x), 128.49 (4x), 127.88 (2x), 56.81 (2x).
4.3.18.
1-Fluoro-2-(4-
fluorobenzenesulfinylmethyl)benzene (6r). Yield = 64%
(161 mg); Colorless solid; mp = 112-113 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
4.3.23.
1-Fluoro-2-
(phenylmethanesulfinylmethyl)benzene (6w). Yield =
78% (193 mg); Colorless solid; mp = 73-75 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C14H14FOS 249.0749, found 249.0752; 1H
NMR (400 MHz, CDCl3): δ 7.30-7.19 (m, 7H), 7.07-6.99
(m, 2H), 3.98 (d, J = 13.2 Hz, 1H), 3.90 (d, J = 13.2 Hz,
1H), 3.81 (d, J = 13.2 Hz, 1H), 3.79 (d, J = 13.2 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 160.48 (d, J = 245.6 Hz),
131.96 (d, J = 3.0 Hz), 129.80, 129.72, 129.65 (2x), 128.34
(2x), 127.79, 124.03 (d, J = 3.8 Hz), 117.28 (d, J = 15.2
Hz), 115.07 (d, J = 21.2 Hz), 57.27, 50.04.
1
C13H11F2OS 253.0499, found 253.0506; H NMR (400
MHz, CDCl3): δ 7.37-7.32 (m, 2H), 7.27-7.21 (m, 1H),
7.08 (d, J = 8.4 Hz, 2H), 7.05-7.02 (m, 2H), 6.94-6.89 (m,
1H), 4.10 (d, J = 12.8 Hz, 1H), 4.01 (d, J = 12.8 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 164.35 (d, J = 250.2 Hz),
160.88 (d, J = 247.1 Hz), 137.86 (d, J = 2.3 Hz), 132.30 (d,
J = 3.8 Hz), 130.23 (d, J = 8.3 Hz), 126.44 (d, J = 8.3 Hz,
2x), 123.96 (d, J = 3.7 Hz), 116.34 (d, J = 15.2 Hz), 116.03
(d, J = 22.0 Hz, 2x), 115.16 (d, J = 22.0 Hz), 56.21; Anal.

ACCEPTED MANUSCRIPT
8
Tetrahedron
163.86, 149.26, 149.15, 143.32, 130.85, 128.67 (2x),
1-Methoxy-3-
4.3.24.
(phenylmethanesulfinylmethyl)benzene (6x). Yield =
126.82, 125.58, 123.80 (2x), 63.26, 59.52, 12.98, 11.04.
77% (200 mg); Colorless gum; HRMS (ESI, M++1) calcd
4.3.30. 2-Benzenesulfinylmethylbenzothiazole (6ad).
Yield = 55% (150 mg); Colorless solid; mp = 108-110 C
1
for C15H17O2S 261.0949, found 261.0954; H NMR (400
o
MHz, CDCl3): δ 7.36-7.23 (m, 6H), 6.87-6.81 (m, 3H),
3.91 (d, J = 13.2 Hz, 1H), 3.87 (d, J = 13.2 Hz, 1H), 3.84
(d, J = 9.6 Hz, 1H), 3.81 (d, J = 9.6 Hz, 1H), 3.75 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 159.57, 131.35, 129.89
(2x), 129.66 (2x), 128.62 (2x), 128.04, 122.05, 115.28,
113.64, 57.07, 57.00, 54.95.
(recrystallized from hexanes and EtOAc); HRMS (ESI,
M++1) calcd for C14H12NOS2 274.0360, found 274.0366;
1H NMR (400 MHz, CDCl3): δ 7.95 (dd, J = 1.2, 8.8 Hz,
1H), 7.80 (dd, J = 1.2 Hz, 8.8 Hz, 1H), 7.55-7.52 (m, 2H),
7.46-7.35 (m, 4H), 7.35 (dt, J = 1.2, 7.2 Hz, 1H), 4.49 (d, J
= 13.6 Hz, 1H), 4.45 (d, J = 13.2 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 158.57, 152.70, 142.21, 135.57, 131.52,
129.12 (2x), 126.18, 125.41, 123.97 (2x), 122.98, 121.41,
60.70.
4.3.25. 1-Phenylmethanesulfinylmethylnaphthalene (6y).
o
Yield = 76% (213 mg); Colorless solid; mp =154-156 C
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C18H17OS 281.1000, found 281.1001; H
4.4. A representative synthetic procedure of skeleton 8
NMR (400 MHz, CDCl3): δ 7.89-7.80 (m, 3H), 7.53-7.30
(m, 9H), 4.46 (d, J = 13.2 Hz, 1H), 4.34 (d, J = 13.2 Hz,
1H), 4.05 (d, J = 12.8 Hz, 1H), 3.98 (d, J = 12.8 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 133.79, 131.64, 130.04
(2x), 129.18, 129.12, 128.84 (2x), 128.78, 128.61, 128.27,
126.61, 126.55, 126.02, 125.33, 123.28, 58.23, 55.96.
is as follows: K2CO3 (460 mg, 3.3 mmol) was added to a
o
solution of 4 (1.0 mmol) in acetone (10 mL) at 25 C. The
o
reaction mixture was stirred at 25 C for 10 min. 2-
Phenylethyl bromide 5p (370 mg, 2.0 mmol) was added to
o
the reaction mixture at 25 C. The reaction mixture was
o
stirred at 57 C for 20 h. The reaction mixture was cooled
to 25 oC and the solvent was concentrated. The residue was
diluted with water (10 mL) and the mixture was extracted
with CH2Cl2 (3 x 20 mL). The combined organic layers
were washed with brine, dried, filtered and evaporated to
afford crude product under reduced pressure. Purification
on silica gel (hexanes/EtOAc = 2/1~1/2) afforded 8 with
two unseparated isomers.
4.3.26. (3-Phenylprop-2-ene-1-sulfinyl)benzene (6z).
Yield = 70% (169 mg); Colorless solid; mp = 84-85 C
o
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C15H15OS 243.0844, found 243.0846; H
NMR (400 MHz, CDCl3): δ 7.62-7.58 (m, 2H), 7.51-7.47
(m, 3H), 7.30-7.21 (m, 5H), 6.41 (d, J = 15.6 Hz, 1H), 5.98
(dt, J = 7.6, 15.6 Hz, 1H), 3.73-3.62 (m, 2H); 13C NMR
(100 MHz, CDCl3): δ 142.76, 138.30, 135.94, 131.03,
128.89 (2x), 128.45 (2x), 128.05, 126.38 (2x), 124.24 (2x),
115.90, 60.57.
4.4.1. (1-Phenylethane-1-sulfinyl)benzene (8a). Two
isomers with a ratio of 3:1; Yield = 21% (48 mg);
Colorless gum; HRMS (ESI, M++1) calcd for C14H15OS
231.0844, found 231.0845; 1H NMR (400 MHz, CDCl3): δ
7.42-7.20 (m, 6H), 7.11-7.09 (m, 1H), 7.01-6.94 (m, 3H),
4.03 (q, J = 7.2 Hz, 1/4H), 3.79 (q, J = 7.2 Hz, 3/4H), 1.68
(d, J = 7.2 Hz, 3/4H), 1.58 (d, J = 7.2 Hz, 9/4H).
4.3.27. 2-Benzenesulfinylmethylpyridine (6aa). Yield =
65% (141 mg); Colorless gum; HRMS (ESI, M++1) calcd
1
for C12H12NOS 218.0640, found 218.0644; H NMR (400
MHz, CDCl3): δ 8.44 (dd, J = 0.8, 8.8 Hz, 1H), 7.54 (dt, J
= 1.6, 7.6 Hz, 1H), 7.45-7.35 (m, 5H), 7.13 (dd, J = 0.8,
8.8 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.16 (d, J = 12.4 Hz,
1H), 4.10 (d, J = 12.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 150.37, 149.49, 142.77, 136.41, 131.00, 128.84
(2x), 125.12, 123.89 (2x), 122.75, 65.30.
4.4.2. 1-Methoxy-3-(1-phenylethane-1-sulfinyl)benzene
(8b). Two isomers with a ratio of 2:1; Yield = 31% (81
mg); Colorless gum; HRMS (ESI, M++1) calcd for
C15H17O2S 261.0949, found 261.0951 1H NMR (400 MHz,
CDCl3): δ 7.27-7.19 (m, 4H), 7.02-6.88 (m, 3H), 6.78-6.70
(m, 5/3H), 6.55-6.54 (m, 1/3H), 3.98 (q, J = 7.2 Hz, 1/3H),
3.80 (q, J = 7.2 Hz, 2/3H), 3.66 (s, 2H), 3.60 (s, 1H), 1.67
(d, J = 7.2 Hz, 2H), 1.60 (d, J = 7.2 Hz, 1H).
4.3.28. 2-Benzenesulfinylmethyl-3,4-dimethoxypyridine
(6ab). Yield = 60% (166 mg); Colorless gum; HRMS (ESI,
M++1) calcd for C14H16NO3S 278.0851, found 278.0855;
1H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 5.6 Hz, 1H),
7.52-7.48 (m, 2H), 7.38-7.35 (m, 3H), 6.70 (d, J = 5.6 Hz,
1H), 4.37 (d, J = 12.4 Hz, 1H), 4.003 (d, J = 12.4 Hz, 1H),
3.78 (s, 3H), 3.67 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
158.46, 145.58 (2x), 144.81, 143.71, 130.87, 128.77 (2x),
123.85 (2x), 107.24, 60.98, 60.44, 55.44.
4.4.3.
1-Fluoro-4-(1-phenylethane-1-sulfinyl)benzene
(8c). Two isomers with a ratio of 2:1; Yield = 15% (37 mg);
Colorless gum; HRMS (ESI, M++1) calcd for C14H14FOS
249.0749, found 249.0746; 1H NMR (400 MHz, CDCl3): δ
7.27-7.14 (m, 4H), 7.06-6.92 (m, 5H), 4.01 (q, J = 7.2 Hz,
1/3H), 3.75 (q, J = 7.2 Hz, 2/3H), 1.68 (d, J = 7.2 Hz, 2H),
1.56 (d, J = 6.8 Hz, 1H).
4.3.29.
2-Benzenesulfinylmethyl-4-methoxy-3,5-
dimethylpyridine (6ac). Yield = 60% (165 mg); Colorless
4.4.4. (1-Phenylethane-1-sulfinylmethyl)benzene (8d).
Two isomers with a ratio of 8:1; Yield = 22% (54 mg);
Colorless gum; HRMS (ESI, M++1) calcd for C15H17OS
245.1000, found 245.1002; For major product: H NMR
(400 MHz, CDCl3): δ 7.41-7.24 (m, 8H), 7.19-7.16 (m,
2H), 3.79 (q, J = 7.2 Hz, 1H), 3.76 (d, J = 12.8 Hz, 1H),
gum; HRMS (ESI, M++1) calcd for C15H18NO2S 276.1058,
1
found 276.1067; H NMR (400 MHz, CDCl3): δ 8.10 (s,
1H), 7.42-7.40 (m, 2H), 7.38-7.33 (m, 3H), 4.33 (d, J =
12.4 Hz, 1H), 3.98 (d, J = 12.8 Hz, 1H), 3.57 (s, 3H), 2.12
(s, 3H), 1.92 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
1

ACCEPTED MANUSCRIPT
Tetrahedron
9
3.59 (d, J = 13.2 Hz, 1H), 1.70 (d, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3): δ 136.64, 130.47, 129.84 (2x),
128.93 (2x), 128.48 (2x), 128.18, 127.90 (2x), 127.83,
61.07, 55.12, 15.32.
Caupene, C.; Boudou, C.; Perrio, S.; Metzner, P. J. Org. Chem. 2005,
70, 2812. For Pd(0), see: (d) Maitro, G.; Prestat, G.; Madec, D.; Poli,
G. J. Org. Chem. 2006, 71, 7449.
(5) The use of β-sulfinyl ester on the Pd2dba3-mediated arylation, see: (a)
Maitro, G.; Vogel, S.; Sadaoul, M.; Prestat, G.; Madec, D.; Poli, G.
Org. Lett. 2007, 9, 5493. (b) Maitro, G.; Vogel, S.; Prestat, G.;
Madec, D.; Poli, G. Org. Lett. 2006, 8, 5951. (c) Maitro, G.; Prestat,
G.; Madec, D.; Poli, G. Synlett 2006, 7, 1055. (d) Maitro, G.; Prestat,
G.; Madec, D.; Poli, G. J. Org. Chem. 2006, 71, 7449. Notably, only
one example (treatment of α-phenylsulfinyl acetone) was reported in
77% yield for overnight.
(6) The use of β-sulfinyl silane, for fluoride-mediated alkylation, see: (a)
Oida, T.; Nakamura, M.; Takashima, Y.; Hayashi, Y. Bull. Inst.
Chem. Res., Kyoto Univ. 1992, 70, 295. For Pd(0)/fluoride-mediated
arylation, see: (b) Jia, T.; Zhang, M.; Jiang, H.; Wang, C. Y.; Walsh,
P. J. J. Am. Chem. Soc. 2015, 137, 13887. (c) Jiang, H.; Jia, T.;
Zhang, T.; Zhang, M.; Walsh, P. J. Org. Lett. 2016, 18, 972.
(7) The use of 2-sulfinyl acrylate on the Pd2dba3-mediated arylation, see:
(a) Singh, S. P.; O’Donnell, J. S.; Schwan, A. L. Org. Biomol. Chem.
2010, 8, 1712. (b) Schwan, A. L.; Verdu, M. J.; Singh, S. P.;
O’Donnell, J. S.; Ahmadi, A. N. J. Org. Chem. 2009, 74, 6851.
(8) The use of allyl aryl sulfoxide precursor on the Pd2dba3-mediated
arylation, see: Bernoud, E.; Le Duc, G.; Bantreil, X.; Prestat, G.;
Madec, D.; Poli, G. Org. Lett. 2010, 12, 320.
(9) The use of aryl benzyl sulfoxide, for the formation of
diarylsulfoxides, see: (a) Jia, T.; Bellomo, A.; Montel, S.; Zhang, M.;
El Baina, K.; Zheng, B.; Walsh, P. J. Angew. Chem. Int. Ed. 2014, 53,
260. (b) Jia, T.; Zhang, M.; Sagamanova, I. K.; Wang, C. Y.; Walsh,
P. J. Org. Lett. 2015, 17, 1168. For the formation of trans-stilbenes,
see: (c) Zhang, M.; Jia, T.; Yin, P.; Carroll, P. J.; Schelter, E. J.;
Walsh, P. J. Angew. Chem. Int. Ed. 2014, 53, 10755. (d) Schwan, A.
L. ChemCatChem 2015, 7, 226. For the formation of
diarylacetylenes, see: (e) Zhang, M.; Jia, T.; wang, C. Y.; Walsh, P. J.
J. Am. Chem. Soc. 2015, 137, 10346.
(10) The use of t-butyl benzyl sulfoxide, for the formation of trans-
stilbenes, see: (a) Zhang, M.; Jia, T.; Sagamanova, I. K.; Pericas, M.
A.; Walsh, P. J. Org. Lett. 2015, 17, 1164. For the formation of
diarylsulfoxides, see: (b) Gelat, F.; Lohier, J.-F.; Gaumont, A.-C.;
Perrio, S. Adv. Synth. Catal. 2015, 357, 2011.
4.5. A synthetic procedure of compounds 6c and 7c is as
follows: (In Table 1, entry 7). K2CO3 (460 mg, 3.3 mmol)
was added to a solution of 4a (245 mg, 1.0 mmol) in
acetone (10 mL) at 25 oC. The reaction mixture was stirred
o
at 25 C for 10 min. 3-Methoxybenzylic bromide 5c (405
mg, 2.0 mmol) was added to the reaction mixture at 25 oC.
o
The reaction mixture was stirred at 57 C for 20 h. The
o
reaction mixture was cooled to 25 C and the solvent was
concentrated. The residue was diluted with water (10 mL)
and the mixture was extracted with CH2Cl2 (3 x 20 mL).
The combined organic layers were washed with brine,
dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexane/EtOAc
= 2/1~1/2) afforded 6c (50%) and 7c (20%).
4.5.1. 3-(3-Methoxyphenyl)-1-phenylpropenone (7c).
Yield = 20% (48 mg); Colorless oil; HRMS (ESI, M++1)
1
calcd for C16H15O2 239.1072, found 239.1076; H NMR
(400 MHz, CDCl3): δ 8.04-8.01 (m, 2H), 7.77 (d, J = 16.0
Hz, 1H), 7.61-7.57 (m, 1H), 7.53-7.49 (m, 3H), 7.34 (t, J =
8.0 Hz, 1H), 7.24 (br d, J = 8.0 Hz, 1H), 7.46 (br t, J = 2.0
Hz, 1H), 6.97 (dd, J = 2.4, 8.4 Hz, 1H), 3.85 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 190.51, 159.89, 144.72,
138.12, 136.20, 132.76, 129.90, 128.59 (2x), 128.46 (2x),
122.33, 121.05, 116.26, 113.38, 55.30.
Acknowledgments
(11) For the sulfenate anion mediated enantio- and diastereoselective
synthesis of sulfoxides, see: (a) Caupene, C.; Boudou, C.; Perrio, S.;
Metzner, P. J. Org. Chem. 2005, 70, 2812. (b) Soderman, S. C.;
Schwan, A. L. Org. Lett. 2011, 13, 4192. (c) Lohier, J.-F.; Foucoin,
F.; Jaffres, P.-A.; Garcia, J. I.; Sopkova-de Oliveira Santos, J.; Perrio,
S.; Metzner, P. Org. Lett. 2008, 10, 1271. (d) Schwan, A. L.; Verdu,
M. J.; Singh, S. P.; O’Donnell, J. S.; Ahmadi, A. N. J. Org. Chem.
2009, 74, 6851.
(12) For reviews on sulfoxide chemistry, see: (a) Wojaczynnska, E.;
Wojaczynnski, J. Chem. Rev. 2010, 110, 4303. (b) O’Mahony, G. E.;
Kelly, P.; Lawrence, S. E.; Maguire, A. R. ARKIVOC 2011, 1, 1. (c)
Bolm, C. Coord. Chem. Rev. 2003, 237, 245.
(13) (a) Pitchen, P.; Dunach, E.; Deshmukh, M. N.; Kagan, H. B. J. Am.
Chem. Soc. 1984, 106, 8188. (b) di Furia, F.; Modena, G.; Seragla, R.
Synthesis 1984, 325.
(14) Andersen, K. K.; Gaffield, W.; Papanikolaou, N. E.; Foley, J. W.;
Perkins, R. I. J. Am. Chem. Soc. 1964, 86, 5637. (b) Senanayake, C.
H.; Krishnamurthy, D.; Lu, Z. H.; Han, Z. X.; Gallou, I.
Aldrichimica Acta 2005, 38, 93.
The authors would like to thank the Ministry of Science
and Technology of the Republic of China for its financial
support (MOST 104-2113-M-037-012). This study is
supported partially by Kaohsiung Medical University “Aim
for the Top Universities Grant, grant No. KMU-
TP104PR15”.
References and notes
(1) For reviews on sulfenate anion chemistry, see: (a) Kharasch, N.;
Potempa, S. J.; Wehrmeister, H. L. Chem. Rev. 1946, 39, 263. (b)
O’Donnell, J. S.; Schwan, A. L. J. Sulfur Chem. 2004, 25, 183. (c)
Maitro, G.; Prestat, G.; Madec. D.; Poli, G. Tetrahedron: Asymmetry
2010, 21, 1075. (d) Schwan, A. L.; Soderman, S. C. Phosphorus,
Sulfur, Silicon Relat. Elem. 2013, 188, 275.
(2) Aversa, M. C.; Bonaccorsi, P.; Madec, D.; Prestat, G.; Poli, G. In
Innovative Catalysis in Organic Synthesis: Oxidation,
Hydrogenation, and C-X Bond Forming Reactions (Ed.: Andersson,
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ACCEPTED MANUSCRIPT
10
Tetrahedron
G.; Xiang, J.; Tian, T.; Huang, Q.; Cun, L.; Liao, J.; Wang, Q.; Zhu,
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