Copper-catalyzed denitrogenative N-arylation of sulfoximines and sulfonamides with arylhydrazines

Article abstract of DOI:10.1016/j.tet.2019.05.039

A Cu-mediated ligand-free arylation of NH-sulfoximines and sulfonamides by arylhydrazine hydrochlorides was herein demonstrated. The oxidative transformation provided an easy access towards N-aryl sulfoximines and sulfonamides in high yields (up to 93% yields) with broad functional groups tolerance (up to 36 examples). The protocol was proposed to take place through the free radical pathway based on the results of control reactions and EPR analysis.

Full text of DOI:10.1016/j.tet.2019.05.039

Accepted Manuscript
Copper-catalyzed denitrogenative N-arylation of sulfoximines and sulfonamides with
arylhydrazines
Wanrong Dong, Chaoyang Liu, Xinchi Ma, Yingjun Zhang, Zhihong Peng, Dexun Xie,
Delie An
PII:
S0040-4020(19)30591-5
https://doi.org/10.1016/j.tet.2019.05.039
TET 30360
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 16 February 2019
Revised Date: 12 May 2019
Accepted Date: 20 May 2019
Please cite this article as: Dong W, Liu C, Ma X, Zhang Y, Peng Z, Xie D, An D, Copper-catalyzed
denitrogenative N-arylation of sulfoximines and sulfonamides with arylhydrazines, Tetrahedron (2019),
doi: https://doi.org/10.1016/j.tet.2019.05.039.
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Copper-Catalyzed Denitrogenative N-
Arylation of Sulfoximines and Sulfonamides
with Arylhydrazines
Leave this area blank for abstract info.
,
a
a
a
b
a
c
,a
Wanrong Dong* , Chaoyang Liu , Xinchi Ma, Yingjun Zhang, Zhihong Peng , Dexun Xie and Delie An*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical
Engineering, Hunan University, Changsha 410082, P. R. China
b
State Key Laboratory of Anti-Infective Drug Development (NO. 2015DQ780357), Sunshine Lake Pharma
Co.,Ltd, Dongguan 523871, P. R. China.
c
Aneo Chem-Tech Co., Ltd, Guangzhou, 510670, PR China

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Copper-Catalyzed Denitrogenative N-Arylation of Sulfoximines and Sulfonamides
with Arylhydrazines
,
a
a
a
b
a
c
Wanrong Dong* , Chaoyang Liu , Xinchi Ma, Yingjun Zhang , Zhihong Peng , Dexun Xie and Delie
An*
,
a
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R.
China
State Key Laboratory of Anti-Infective Drug Development (NO. 2015DQ780357), Sunshine Lake Pharma Co.,Ltd, Dongguan 523871, P. R. China.
b
c
Aneo Chem-Tech Co., Ltd, Guangzhou, 510670, PR China
Emails: wanrongdong@hnu.edu.cn; deliean@hnu.edu.cn.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A Cu-mediated ligand-free arylation of NH-sulfoximines and sulfonamides by arylhydrazine
hydrochlorides was herein demonstrated. The oxidative transformation provided an easy access
towards N-aryl sulfoximines and sulfonamides in high yields (up to 93% yields) with broad
functional groups tolerance (up to 36 examples). The protocol was proposed to take place
through the free radical pathway based on the results of control reactions and EPR analysis.
Available online
2
009 Elsevier Ltd. All rights reserved.
Keywords:
Copper catalysis
Dehydrogenative arylation
Arylhydrazines
NH-Sulfoximines
Sulfonamides
Introduction
atmosphere. Along this line, methods for the preparations of
diaryls and N-aryl amines, have been successfully achieved in the
NH-Sulfoximines and sulfonamides, which took possession of
analogous structures, have attracted widespread research interests
for the unique architectures, as well as for extensive applications
presence of different transition metallic catalysts through the
[16-19]
denitrogenation pathway.
Inspired by the fruitful results and
[20]
the denitrogenation protocols
for the formations of arylated
[
1]
in the pharmaceutical and organic synthetic communities. Great
development has been broadly witnessed for the past decade and
different methodologies have been widely documented for the N-
functionalization of the useful building blocks. For example,
straightforward N-arylation of sulfoximines has been successfully
anilines (Co/Cu-cocatalyzed system), and successful desulfitative
arylation of NH-sulfoximines and sulfonamides from our
[21]
group,
we wished to disclosed another practical and facile
transformation toward N-aryl sulfoximines and sulfonamides
mediated by copper-catalysts under oxidative conditions, in
which arylhydrazines participated as an efficient aryl donor in the
system.
[
2]
[3]
achieved, using aryl halides, aryl triflates, aryl boronic
[
4]
[5]
[6]
[7]
acids, aryl siloxanes, diaryl iodonium salts, arynes and
etc. as the aryl donors, while direct N-aryl sulfonamides have
been prepared with the employments of aryl halides, aryl
[
8]
[
9]
Results and Discussion
[
10]
[11]
[12]
boronic acids,
aryl [14]siloxanes,
aryl nonaflates,
[
13]
The investigation began with the optimization of the
conditions for the arylation protocol with S-phenyl-S-methyl
sulfoximine (1a) and phenylhydrazine hydrochloride (2a) as
model substrates, which were summarized in the Table 1. To our
cyclohexanones and etc as the aryl sacrifices in the system.
However, novel transformations towards N-aryl sulfoximines and
sulfonamides are still severely demanded as the intrinsic
requirement for the development of the chemistry discipline.
[
15]
satisfaction, Cu(OAc) was capable to make the reaction take
Arylhydrazines, which came into our visual field, have been
regarded as an excellent arylation reagent through the C-N bond
2
place in the presence of Cs CO as the base in acetonitrile in the
2
3
dioxygen atmosphere, providing 3aa in 37% yield at room
temperature for 12 hours (entry 1). Other inorganic bases,
including K CO (entry 2), Na CO (entry 3), KOAc (potassium
cleavage, releasing N as the byproduct. Despite of the limited
2
substrate scope, arylhydrazines still remained attractive in the
field of the synthetic chemistry, for they are able to undergo the
oxidative conditions for the generations of the aryl radicals
through SET (single electron transfer) process via highly unstable
aryldiazene intermediates, even under the molecular oxygen
2
3
2
3
acetate for entry 4), K PO4 (entry 5) rendered the arylation
3
protocol occur at room temperature, giving the desired N-phenyl
sulfoximine (3aa) in yields from 20% to 48%. But oppositely,
organic
bases
including pyridine
(entry 6),
1,8-

2
Tetrahedron
diazabicyclo[5.4.0]undec-7-ene (DBU for en
A
try
C
7
C
) a
E
nd
P
t
T
rie
E
th
D
yl MAen
NU
try
1
S
8
C
),
R
N,
I
N-dimethyl formamide (DMF for entry 20) and
P
T
amine (entry 8) showed negative effects to the transformation
and only trace of 3aa was detected at room temperature for 36
hours. Other cupric catalysts, such as Cu(TFA) (TFA for
trifluoroacetate, entry 9), CuSO (entry 10), Cu(OTf) (entry 11),
CuCl (entry 12) and CuBr (entry 13), Cu(acac) (entry 14) all
performed positively in the system for the generation of 3aa, but
without significant improvement to the transformation.
dimethyl sulfoxide (DMSO for entry 21), because the highest
92% yield of 3aa was successfully separated when the reaction
was conducted in acetone. Effect of external oxidants was also
examined under the argon atmosphere. Surprisingly, the reaction
between 1a and 2a finished in 2 hours in the presence of TBHP
(70% in decane), furnishing 3aa in 70% yield (entry 22). But di-
tert-butyl peroxide (entry 23) gave only trace 3aa while
2
4
2
2
2
2
a
PhI(OAc) (entry 24) and 2-iodoxybenzoic acid (IBX for entry 25)
2
Table 1. Optimization of Reaction Conditions
furnished 3aa in medium yields within 2 hours. The key role of
the cupper catalyst in the reaction was proved when the reaction
was carried out in the absence of the catalyst and no reaction was
detected (entry 26).
With the optimal conditions in hands, evaluation for the substrate
scope and limitations of the protocol was then carried out as
shown in Table 2. For NH-sulfoximines, S-tolyl-S-methyl
sulfoximines were all compatible well in the system and
positions of the methyl group had slight influence on the
efficiency of the transformation, for S-(2-tolyl)-S-methyl-N-
phenyl sulfoximine (3ba) were obtained in 75% yield (entry 1),
while S-(3-tolyl)-S-methyl-N-phenyl sulfoximine (3ca) and S-(4-
tolyl)-S-methyl-N-phenyl sulfoximine (3da) were furnished in
b
Entry
Cat.
Base
Cs CO
CO
CO
[O]
Sol.
CH CN
Yield
37%
42%
30%
48%
20%
trace
trace
trace
30%
32%
58%
37%
30%
40%
58%
70%
62%
trace
92%
trace
1
2
3
4
5
6
7
8
9
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
2
2
2
2
2
3
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
K
2
3
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
Na
2
3
KOAc
PO
K
3
4
8
5% and 90% yields, respectively (entries 2 and 3). Similarly, S-
Pyridine
DBU
(4-methoxypheny)-S-methyl-N-phenyl sulfoximine (3ea) was
isolated in 88% yield after 12 h (entry 4). However, S-(4-
chlorophenyl)-S-methyl-N-phenyl sulfoximine (3fa) was also
provided in 93% yield, higher than electron-sufficient phenyl
substituted NH-sulfoximines (entry 5). Then, exploration for the
scope of arylhydrazines was conducted in the CuBr-mediated
system under the mild conditions. Satisfyingly, 2-tolyl hydrazine
hydrochloride (2b) coupled with sulfoximine 1a successfully,
forming the corresponding N-aryl sulfoximine 3ab in 76% yield
(entry 6). However, 4-tolyl hydrazine hydrochloride (2c) allowed
the formation of 3ac in 90% yield (entry 7), while 4-tert-
butylphenyl (2d) and 4-methoxyphenyl (2e) hydrazine
hydrochloride reacted with 1a smoothly, giving the desired N-
arylated product 3ad and 3ae in 82% and 79% yields, separately
NEt
3
Cu(TFA)
2
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
CuSO
4
Cu(OTf)
CuCl
CuBr
2
2
2
Cu(acac)
CuCl
CuBr
CuI
2
(
entries 8 and 9). Halo substituted arylhydrazines were also
tolerated in the system. 4-Fluoro- (entry 10), 2-chloro- (entry 11),
-chloro- (entry 12), 4-chloro- (entry 13), 2-bromo- (entry 14), 3-
3
bromo- (entry 15), 4-bromo- (entry 16) and 4-iodo- (entry 17)
phenyl hydrazine hydrochlorides coupled with 1a successfully,
furnishing the desired products 3af – 3am in yields from 73% -
89%. It was noteworthy that the positions of the halo groups did
not affect the efficiency of the transformation significantly by the
comparison between entries 11 – 13 and entries 14 – 16.
Electron-deficient arylhydrazine hydrochlorides, which were
exemplified by 4-cyanophenyl (2n for entry 18) and 4-
trifluoromethylphenyl (2o for entry 19) underwent the arylation
protocol, forming 3an and 3ao in 90% and 82% yields,
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr
-
THF
c
1
9
acetone
DMF
2
2
0
1
d
DMSO
acetone
acetone
acetone
acetone
acetone
n.d.
e
2
2
TBHP
DTBP
70%
trace
72%
58%
n.d.
2
3
respectively.
hydrochloride (2p) rendered the formation of 3ap in 88% yield
entry 20).
Polyaryl,
such
as
2-naphthylhydrazine
e
2
4
5
PhI(OAc)
2
e
(
2
IBX
a
Table 2. Substrate Scope of Preparation of N-Aryl Sulfoximines
2
6
O
2
a
Reaction conditions: 1a (0.3 mmol), 2a (0.6 mmol), Cat. (20 mol%), [O]
0.6 mmol), Base (0.6 mmol) under air in Sol. (1.5 mL) at room
(
b
c
d
temperature for 12 h. Isolated yields. the optimal conditions. for not
detected. the reaction finished in 2 hours according to TLC analysis.
e
Cuprous salts, like CuCl (entry 15), CuBr (entry 16) and CuI
1
2
b
Entry
Ar (1)
Ar (2)
3
Yield
75%
85%
(entry 17) offered noteworthy increase in the efficiency of the
protocol for the yields of 3aa were obtained up to 70% (by CuBr
for entry 16). Screening on the suitable solvent were
subsequently embarked and acetone (entry 19) distinguished
from the other solvents tested, such as tetrahydrofuran (THF for
1
2
2-CH C H (1b)
Ph (2a)
Ph (2a)
3ba
3ca
3
6
4
3 6 4
3-CH C H (1c)

3
1
1
C
6
H
5
(4a)
4-FC
6
H
4
(2f)
5af
5ai
72%
65%
60%
62%
69%
3
4
5
6
7
8
9
4-CH
3
C
6
H
4
(1d)
(1e)
Ph (2a)
Ph (2a)
Ph (2a)
A
3
C
daCEPT90
E
%
D MANUSCRIPT
1
1
1
1
2
3
4
5
C
C
C
C
6
6
6
6
H
5
H
5
H
5
H
5
(4a)
(4a)
(4a)
(4a)
4-ClC
6
H
4
(2i)
(2l)
(2n)
4-CH
3
OC
6
H
4
3ea
88%
93%
76%
90%
82%
79%
81%
73%
85%
87%
75%
82%
89%
86%
90%
82%
88%
4-BrC
6
H
4
5al
4-ClC
6
4
H (1f)
3fa
4-CNC
6
H
4
5an
5ap
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
(1a)
2-CH
4-CH
4-tBuC
4-CH OC
3
C
6
H
4
(2b)
(2c)
(2d)
3ab
3ac
3ad
3ae
3af
2-Naphthyl (2p)
3 6 4
C H
a
Reaction conditions: 1 (0.5 mmol), 2 (1.0 mmol), Cu(acac)
TBHP (1.0 mmol), Cs CO b(1.0 mmol) in sealed tube under air in CH
4.0 mL) at 100 C for 12 h. Isolated yields.
2
(20 mol%),
CN
6
H
4
2
3
3
o
(
3
6 4
H (2e)
To our delight, phenyl sulfonamide (4a) reacted with 2a
successfully, giving the phenylated product 5aa in 68% yield
entry 1). Tolyl sulfonamides, exemplified by 2-tolyl (4b for
entry 2) and 3-tolyl (4c for entry 3) sulfonamides were also easily
arylated in the Cu(acac) -mediated system and positions of the
methyl group on the substrates showed slight effects on the
produce of 5ba and 5ca in similar yields. Halophenyl
sulfonamides, such as 4-fluorophenyl sulfonamide (4d), 4-
chlorophenyl sulfonamide (4e) and 4-bromophenyl sulfonamide
4f) with phenylhydrazine hydrochloride (2a), constructing the
desired products 5da – 5fa in yields from 70% to 78% (entries 4
6). Electron-deficient sulfonamide, like 4-trifloromethylphenyl
sulfonamide (4g) coupled with 2a and 5ga was readily isolated in
9% yield (entry 7). In a similar pattern, compatibilities of the
1
0
1
2
3
4
5
6
7
8
9
0
4-FC
6
H
4
(2f)
(2g)
(2h)
(
1
1
1
1
1
1
1
1
1
2
2-ClC
6
H
4
3ag
3ah
3ai
3-ClC
6
H
4
2
4-ClC
2-BrC
6
6
H
4
(2i)
(2j)
(2k)
(2l)
H
4
3aj
3-BrC
6
H
4
3ak
3al
(
4-BrC
6
H
4
–
4-IC
4-CNC
4-CF
6
H
4
(2m)
3am
3an
3ao
3ap
6
6
H
4
(2n)
(2o)
substituted arylhydrazines hydrochlorides were also explored in
the Cu(acac) -catalyzed practice. At elevated temperature, good
3
C
6
H
4
2
tolerance was witnessed and 2- or 3-methyl- (2b and 2c for
entries 8 and 9), 4-methoxy- (2d for entry 10), 4-fluoro- (2f for
entry 11), 4-chloro- (2i for entry 12), 4-bromo- (2l for entry 13)
and 4-cyano- (2n for entry 14) and 2-naphthyl- (2p for entry 15)
hydrazine hydrochlorides reacted with sulfonamide 4a favorably,
forming the desired arylated sulfonamides in yields from 58% to
2-Naphthyl (2p)
a
Reaction conditions: 1 (0.5 mmol), 2 (1.0 mmol), CuBr (20 mol%), KOAc
1.0 mmol) under O atmosphere in acetone (4.0 mL) at room temperature for
2 h. Isolated yields.
(
1
2
b
7
2%.
Inspired by the broad substrate scope and high efficiency of
the arylation protocol between NH-sulfoximines and
arylhydrazine hydrochlorides, investigation of the transformation
was further extended on sulfonamides, which possessed
analogous structure with NH-sulfoximines (Table 3). However,
simple transferring the conditions onto the arylation of
To have a deeper insight into the arylation protocol,
competitive reactions were conducted for distinguishing the
reactivities of arylhydrazine hydrochloride bearing different
functional groups, as shown in Scheme 1.
O
S
CH3
NH
O
S
CH3
N
sulfonamides failed, and the participation of Cu(acac) as the
2
NHNH —HCl
2
CuBr, KOAc
+
Eq. 1
R
catalyst, Cs CO as the base, CH CN as the solvent was proved
2
3
3
acetone, O2
r.t., 12 h
R
crucial to the transformation. Moreover, elevated temperature
o
2
2
2
c/2e (R = CH3, or OCH3);
i/2o (R = Cl, or CF3);
c/2o (R = CH3, or CF3)
3ac/3ae = 1:0.73;
3ai/3ao = 0.9:1;
3ac/3ao = 0.36:1
(
100 C) was also important for the completion of the reaction.
a
Table 3. Substrate Scope of Preparation of N-Aryl Sulfonamides
O
O
CH3
NH
O
S
CH3
N
CuBr
S
NHNH2
+
+
Eq. 2
Eq. 3
acetone, O2
r.t., 24 h
3
aa, 50% yield
TEMPO (2.0 equiv.)
NHNH2—HCl CuBr, KOAc
O
S
CH3
NH
CH3
N
S
acetone, O2
r.t., 12 h
1
2
b
Entry
Ar (4)
Ar (2)
5
Yield
68%
62%
65%
70%
75%
78%
69%
62%
66%
58%
3aa, trace
1
2
3
4
5
6
7
8
9
C
6
H
5
(4a)
C
C
C
C
C
C
C
6
6
6
6
6
6
6
H
5
H
5
H
5
H
5
H
5
H
5
H
5
(2a)
(2a)
(2a)
(2a)
(2a)
(2a)
(2a)
5aa
5ba
5ca
5da
5ea
5fa
5ga
5ab
5ac
5ae
Scheme 1. Competitive and Control Reactions
2-CH
3-CH
4-FC
4-ClC
4-BrC
4-CF
3
C
6
H
4
(4b)
(4c)
For instance, a mixture of p-tolyl hydrazine hydrochloride (2c)
and p-methoxyphenylhydrazine hydrochloride (2e) reacted with
NH-sulfoximine 1a smoothly for 12 hours, forming a mixture of
3
6 4
C H
6
4
H (4d)
1
6
H
4
(4e)
(4f)
3ac and 3ae in 1:0.73 ratio according to crude H-NMR (Eq. 1).
In a same manner, a mixture of 2i and 2o coupled with 1a
successfully, offering the corresponding arylated sulfoximines
6
H
4
3
6 5
C H (4g)
3
ai and 3ao in 0.9:1 ratio. However, the difference between
C
C
C
6
6
6
H
H
H
5
(4a)
(4a)
(4a)
2-CH
4- CH
4-CH OC
3
C
6
H
4
(2b)
(2c)
electron-sufficient and electron-deficient arylhydrazines was
declared by the employment of 2c and 2o, for formation of a
mixture of 3ac and 3ao was isolated successfully after 12 hours,
in 0.36:1 ratio. It assumed that the electron-deficient substrates
5
5
3
C
6
H
4
1
0
3
6 4
H (2e)

4
Tetrahedron
offered higher performance which probably d
effect.
A
ue
C
to
C
t
E
he
P
e
T
lec
E
tron MA(λ
D
NU
=
25
S
4
C
nm
R
).
I
F
P
o
T
r flash column chromatography, silica gel (200 -
300 mesh) was used as stationary phase and a mixture of n-
1
13
hexane and ethyl acetate was used as eluent. H and C NMR
spectra were recorded on a Varian INOVA-400 in deuterated
chloroform at 25 °C with residue solvent peaks as internal
Subsequently, the reaction between 1a and phenylhydrazine
was conducted for clearance of the role of KOAc in the protocol
(Eq. 2). However, the reaction completed within 24 hours on the
1
13
standards (δ = 7.26 ppm for H-NMR and δ = 77.16 ppm for C-
NMR). Chemical shifts δ are reported in ppm, and spin-spin
coupling constants (J) are given in Hz, while multiplicities are
abbreviated by s (singlet), d (doublet), t (triplet), q (quartet) and
m (multiplet). Mass spectra were recorded on a ThermoFinnigan
MAT95XP microspectrometer and High Resolution Mass
Spectra (HRMS) were recorded on Agilent Technologies
Accurate Mass Q-TOF 6530 microspectrometer. Melting points
were recorded on a national standard melting point apparatus
(Model: Taike XT-4) and were uncorrected.
consumption of the hydrazine, furnishing the desired aryl
sulfoximine 3aa in ca. 50% yields, probably due to the
homocoupling of 2a. Addition of radical scavenger TEMPO
(2,2,6,6-tetramethylpiperidine-1-oxide) depressed the formation
of 3aa dramatically, for only trace 3aa were checked aftere 12
hours (Eq. 3). This indicated the denitrogenative transformation
might take place through a free radical pathway.
Successively, EPR (Electron Paramagnetic Resonance)
analysis was conducted to find more information on the possible
radical protocol, as exemplified by the reaction between 1a and
[
22]
General procedure towards N-aryl sulfoximines 3
2
a.
To our satisfaction, 2a gave expected signal in the
presence of KOAc (2.0 equiv.) under O atmosphere in acetone,
Under the oxygen atmosphere, a Schlenk tube (35 mL) equipped
2
giving a g factor as 2.00237 (in a range of 2.0020 - 2.0025 for
with a magnetic bar was loaded with the NH-sulfoximine 1 (0.5
e
aryl radicals). (P185) Based on the EPR analysis and literature
explorations, mechanism of the newly-developed method was
proposed by the reaction between 1a and 2a, via an aryl radical
intermediate, which probably was generated in situ from
arylhydrazine hydrochloride in the dioxygen atmosphere
mmo), arylhydrazine chloride (2.0 equiv.), Cu(OAc) (20 mol%),
2
KOAc (2.0 equiv.) in dry acetone (4.0 mL). Then the mixture
was allowed to stir at room temperature for 12 hours. After the
completion of the reaction, as monitored by TLC analysis, the
mixture was filtered through a short celite pad and washed with
dichloromethane (15 mL × 3). The filtrate was concentrated, and
the oily crude product was purified by column chromatography
using silica gel (200 – 300 mesh) as stationary phase and a
mixture of n-hexane and ethyl acetate (2:1) as eluent to give the
(Scheme 3). In the presence of KOAc, phenylhydrazine was
easily generated in situ. And successive oxidation step took place
on the phenylhydrazine, offering another key intermediate
phenyldiazene (A) with a release of H O. Upon the interaction
2
with molecular oxygen, the intermediate B was transformed
quickly into phenyldiazene radical C. Along the emission of
nitrogen gas, phenyl radical D was formed, which could couple
with sulfoximine (1a)-liganded Cu(II) complex easily to afford
another key Cu(III)-cored intermediate E. Then the desired
product 3aa was formed along with an elimination step, giving
Cu(I) species, which could be reoxidized into another Cu(II)
under the oxidative atmosphere for the next circle.
corresponding arylated products 3 or 5 (R = ca.0.3 otherwise
noted).
f
General procedure towards N-aryl sulfonamides 5
Under the air atmosphere, a Schlenk tube (35 mL) equipped with
a magnetic bar was loaded with the sulfonamide 4 (0.5 mmol),
Cu(acac) (20 mol%), TBHP (70% in water, 2.0 equiv.), Cs CO
2
2
3
(2.0 equiv.) in dry solvent MeCN (4.0 mL). Then the reaction
o
mixture was allowed to stir at 60 C for 12 hours. After the
completion of the reaction, as monitored by TLC analysis, the
mixture was filtered through a short celite pad and washed with
dichloromethane (15 mL × 3). The filtrate was concentrated, and
the oily crude product was purified by column chromatography
using silica gel (200 – 300 mesh) as stationary phase and a
mixture of n-hexane and ethyl acetate (2:1) as eluent to give the
corresponding arylated products 5 (R = ca.0.3 otherwise noted).
f
N,S-Diphenyl-S-methyl sulfoximine (3aa): white solid (72.8 mg,
1
9
7
2
7
2% yield), m.p. 95 - 96 °C. H NMR (400 MHz, CDCl ): δ =
3
.98 (d, J = 7.3 Hz, 2H), 7.60-7.55 (m, 1H), 7.52 (t, J = 7.3 Hz,
H), 7.12 (t, J = 7.7 Hz, 2H), 7.01 (d, J = 7.6 Hz, 2H), 6.87 (t, J =
.2 Hz, 1H), 3.23 (s, 3H) (ppm). C NMR (100MHz, CDCl ): δ
13
3
=
145.1, 139.6, 133.3, 129.6, 129.1, 128.7, 123.4, 121.8, 46.1
(ppm). IR (KBr): ν = 3057, 3015, 2970, 2914, 2342, 1930, 1594,
1
6
7
2
486, 1415, 1354, 1267, 1202, 1093, 1040, 973, 830, 756, 672,
-1
Scheme 3. Plausible Mechanism
23, 550 (cm ). MS (ESI): m/z (%) = 231.0, 140.0, 138.0, 91.0,
+
In conclusion, we have disclosed a practical and facile N-
arylation of sulfoximines and sulfonamides using arylhydrazine
hydrochlorides with assistance of a Cu(II)-catalyst under
oxidative conditions. The method provided
methodology towards various N-aryl sulfoximines and
7.0. HRMS (ESI-TOF) m/z: [M+H] Calcd for C H NOS
1
3
14
32.0791; Found 232.0789.
N-Phenyl-S-(2-methylphenyl)-S-methyl
Colorless thick oil (55.1 mg, 75% yield). H NMR (400 MHz,
CDCl ): δ = 8.15 (d, J = 7.9 Hz, 1H), 7.44 (t, J = 7.4 Hz, 1H),
7
6
2
1
4
1
9
Sulfoximine
(3ba):
a
general
1
sulfonamides of great significance with high efficiency.
3
.35 (t, J = 7.6 Hz, 1H), 7.25 (s, 1H), 7.09 (t, J = 7.5 Hz, 2H),
.96 (d, J = 7.6 Hz, 2H), 6.84 (t, J = 7.3 Hz, 1H), 3.26 (s, 3H),
General Remarks
13
.66 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ = 145.3,
All product mixtures were analyzed by thin layer
chromatography glass-backed silica TLC plates with
fluorescent indicator from Branch of Qingdao Haiyang Chemical
CO. LTD. UV-active compounds were detected with a UV lamp
3
37.8, 137.7, 133.4, 133.2, 131.4, 129.1, 127.0, 122.7, 121.6,
4.8, 20.7 (ppm). IR (KBr): ν = 3057, 3027, 2954, 2930, 2340,
914, 1594, 1488, 1432, 1309, 1266, 1204, 1069, 1034, 1009,
a
-
1
89, 956, 832, 731, 685, 601, 549 (cm ). MS (ESI): m/z (%) =

5
2
45.1 (100), 182.1, 167.1, 154.0, 107.0. HRMS
A
(
C
ES
C
I-T
E
O
P
F
T
):
E
m
D
/z: MA
=
N
30
U
20
S
, 2
C
96
R
1,
I
2
P
9
T
23, 2360, 1905, 1573, 1505, 1446, 1318, 1287,
+
[
M+H] Calcd for C H NOS 246.0947; Found. 246.0950.
1263, 1203, 1094, 1069, 1034, 1012, 994, 824, 746, 688, 612,
32 (cm ). MS (ESI): m/z (%) = 245.1 (100), 141.0, 118.1,
14
16
-
1
5
N-Phenyl-S-(3-methylphenyl)-S-methyl
Colorless thick oil (62.5 mg, 85%). H NMR (400 MHz, CDCl ):
δ = 7.80 (s, 1H), 7.76 (d, J = 6.2 Hz, 1H), 7.42 - 7.36 (m, 2H),
Sulfoximine
(3ca):
+
1
106.1. HRMS (ESI-TOF) m/z: [M+H] Calcd for C14
46.0947; found: 246.0944.
H16NOS
3
2
7
.13 (t, J = 7.5 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H), 6.87 (t, J = 7.3
N-(4-tert-Butylphenyl)-S-methyl-S-phenyl Sulfoximine (3ad):
13
1
Hz, 1H), 3.22 (s, 3H), 2.41 (s, 3H) (ppm). C NMR (100 MHz,
Yellowish oil (70.6 mg, 82%). H NMR (400 MHz, CDCl ): δ =
3
CDCl ) δ = 145.2, 139.9, 139.5, 134.2, 129.5, 129.1, 129.1,
7.99 (d, J = 7.3 Hz, 2H), 7.58 (t, J = 7.3Hz, 1H), 7.52 (t, J = 7.4
Hz, 2H), 7.14 (d, J = 8.6 Hz, 2H), 6.93 (d, J =8.6 Hz, 2H), 3.21
3
1
2
1
25.8, 123.4, 121.8, 46.1, 21.5 (ppm). IR (KBr): ν = 3078, 3026,
13
978, 2926, 2312, 1924, 1594, 1487, 1436, 1301, 1291, 1266,
(s, 3H), 1.23 (s, 9H) (ppm). C NMR (100 MHz, CDCl ): δ =
3
-
1
094, 1040, 980, 954, 833, 745, 840, 610, 544 (cm ). MS (ESI):
144.4, 142.1, 139.9, 133.2, 129.6, 128.7, 125.9, 122.8, 46.1, 34.1,
31.5 (ppm). IR (KBr): ν = 3029, 2961, 2925, 2364, 1901, 1605,
1578, 1505, 1446, 1317, 1291, 1204, 1095, 1036, 1019, 969, 825,
m/z (%) = 246.1, 139.1, 108.1, 92.1 (100). HRMS (ESI-TOF):
+
m/z: [M+H] Calcd for C H NOS 246.0947; Found. 246.0945.
14
16
-
1
6
90, 603, 521 (cm ). MS (ESI): m/z (%) = 287.1, 272.1 (100),
N-Phenyl-S-(4-methylphenyl)-S-methyl
Colorless thick oil (66.1 mg, 90%). H-NMR (400 MHz, CDCl ):
Sulfoximine
(3da):
+
1
180.1. HRMS (ESI-TOF) m/z: [M+H] Calcd for C17
88.1417; found: 288.1421.
H22NOS
3
2
δ = 7.84 (d, J = 7.5 Hz, 2H), 7.31 (d, J = 7.7Hz, 2H), 7.11 (t, J =
7
3
.4 Hz, 2H), 7.00 (d, J = 7.7 Hz, 2H), 6.86 (t, J =7.3 Hz, 1H),
N-(4-Methoxyphenyl)-S-phenyl-S-methyl Sulfoximine (3ae):
White solid (61.9 mg, 79%), m.p. 102 - 103 °C. H NMR (400
13
1
.22 (s, 3H), 2.40 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ
3
=
145.3, 144.3, 136.5, 130.3, 129.1, 128.8, 123.4, 121.7, 46.3,
MHz, CDCl ): δ = 7.97(d, J = 7.3 Hz, 2H), 7.58 (t, J = 7.3 Hz,
3
2
1
7
1
1.7 (ppm). IR (KBr): ν = 3074, 3026, 2956, 2925, 2359, 1908,
1H), 7.52 (t, J = 7.5 Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H), 6.68 (d, J
= 8.9 Hz, 2H), 3.70 (s, 3H), 3.21 (s, 3H) (ppm). C NMR (100
13
594, 1487, 1449, 1315, 1266, 1204, 1199, 1093, 1012, 995, 826,
-
1
49, 688, 605, 521 (cm ). MS (ESI): m/z (%) = 245.1 (100),
MHz, CDCl ): δ = 154.9, 139.6, 138.0, 133.3, 129.6, 128.8,
3
+
82.1, 167.1, 138.1, 91.1, 65.1. HRMS (ESI-TOF): m/z: [M+H]
124.5, 114.5, 55.5, 45.8 (ppm). IR (KBr): ν =3026, 3002, 2967,
Calcd for C H NOS 246.0947; Found: 246.0949.
2929, 2833, 1910, 1503, 1444, 1325, 1263, 1237, 1042, 1006,
14
16
-
1
9
76, 826, 746, 635, 535 (cm ). MS (ESI): m/z (%) = 261.0,
N-Phenyl-S-(4-methoxyphenyl)-S-methyl Sulfoximine (3ea):
1
179.0 (100), 154.0, 121.0, 107.0, 91.0. HRMS (ESI-TOF) m/z:
Colorless oil (68.9 mg, 88%). H NMR (400 MHz, CDCl ): δ =
+
3
[
M+H] Calcd for C H NO S 262.0896; found: 262.0898.
14 16 2
7
.89 (d, J = 8.9 Hz, 2H), 7.12 (t, J = 7.8Hz, 2H), 7.01 (d, J = 7.5
Hz, 2H), 6.97 (d, J = 8.9 Hz, 2H), 6.87 (t, J =7.3 Hz, 1H), 3.84 (s,
N-(4-Fluorophenyl)-S-phenyl-S-methyl Sulfoximine (3af): White
solid (113.3 mg, 91%), m.p. 82 - 83 °C. H NMR (400 MHz,
13
1
3
1
H), 3.22 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ = 163.5,
45.3, 130.9, 130.7, 129.1, 123.4, 121.7, 114.9, 55.7, 46.6 (ppm).
3
CDCl ): δ = 7.94 (d, J = 7.1 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H),
3
IR (KBr): ν = 3016, 2960, 2928, 2842, 1589, 1481, 1439, 1291,
7.52 (t, J = 7.5 Hz, 2H), 6.95 (dd, J = 9.0, 4.9 Hz, 2H), 6.80 (t, J
= 8.7 Hz, 2H), 3.22 (s, 3H) (ppm). C NMR (100 MHz, CDCl3):
-
1
13
1
260, 1187, 1095, 1036, 869, 812, 740, 685, 647, 611, 549(cm ).
MS (ESI): m/z = 262.1 (100), 118.1. HRMS (ESI-TOF): m/z:
δ = 158.4 (JC-F = 238.5 Hz), 141.0, 139.2, 133.4, 129.7, 128.7,
+
19
[
M+H] Calcd for C H NO S 262.0896; found. 262.0895.
124.5 (JC-F = 7.8 Hz), 115.6 (JC-F= 22.0 Hz), 46.0 (ppm).
F
14
16
2
NMR (370 MHz, CDCl ): δ = -122.3 (ppm). IR (KBr): ν = 3063,
3
N-Phenyl-S-(4-chlorophenyl)-S-methyl
Yellowish oil (73.9 mg, 93%). H NMR(400 MHz, CDCl ): δ =
Sulfoximine
(3fa):
1
3024, 2964, 2928, 2365, 1907, 1574, 1445, 1318, 1291, 1263,
3
-1
1
208, 1093, 1032, 1015, 995, 820, 746, 689, 611, 540 (cm ). MS
7
.90 (d, J = 8.6 Hz, 2H), 7.48 (d, J = 8.6 Hz,2H), 7.13 (t, J = 7.9
(
ESI): m/z (%) = 249.1 (100), 186.1, 124.1, 109.1, 77.1. HRMS
Hz, 2H), 6.99 (d, J = 7.5 Hz, 2H), 6.89 (t, J = 7.4Hz, 1H), 3.23 (s,
+
1
3
(ESI-TOF) m/z: [M+H] Calcd for C13
found: 250.0693.
H13FNOS 250.0696;
3
1
3
1
H) (ppm). C NMR (100 MHz, CDCl ): δ =144.7, 140.0, 138.0,
3
30.3, 129.9 129.2, 123.4, 122.1, 46.2 (ppm). IR (KBr): ν =
081, 3027, 2967, 2927, 2360, 1904, 1578, 1485, 1324, 1290,
267, 1090, 1084, 1041, 1015, 995, 962, 831, 749, 680, 611, 535
cm ). MS (ESI): m/z = 266.0 (100), 218.1, 157.0. HRMS (ESI-
TOF): m/z: [M+H] Calcd for C H ClNOS 266.0401; found:
N-(2-Chlorophenyl)-S-methyl-S-phenyl Sulfoximine (3ag): White
1
solid (58 mg, 79%), m.p. 61 - 62 °C, H NMR (400 MHz,
-
1
(
CDCl ): δ = 8.04 (d, J = 7.6 Hz, 2H), 7.61-7.56 (m, 1H), 7.52 (t,
3
+
J = 7.3 Hz, 2H), 7.30 (d, J = 7.9 Hz, 1H), 7.18 (d, J = 8.0 Hz,
1H), 6.96 (t, J = 7.5 Hz, 1H), 6.81 (t, J = 7.5 Hz, 1H), 3.24 (s,
13
13
2
66.0405.
13
3
H) (ppm). C NMR (100 MHz, CDCl ): δ = 142.2, 139.1,133.5,
3
N-(2-Methylphenyl)-S-methyl-S-phenyl Sulfoximine (3ab): White
solid (55.9 mg, 76%), m.p. 62 - 63 °C. H NMR (500 MHz,
1
129.9, 129.6, 128.6, 127.2, 124.0, 122.8, 45.7 (ppm). IR (KBr): ν
3012, 2922, 1639, 1477, 1308, 1198, 1098, 1027, 747, 683,
=
CDCl ): δ = 7.99 (d, J = 7.2 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H),
-1
3
5
9
19(cm ). MS (ESI): m/z (%) = 265.0, 202.1, 167.1 (100), 124.1,
2.1, 77.0. HRMS (ESI-TOF) m/z: [M+H] Calcd for
7
.53 (t, J = 7.5 Hz, 2H), 7.12 (d, J = 7.1 Hz, 1H),7.01 (d, J = 7.3
+
Hz, 1H), 6.92 (t, J = 7.6 Hz, 1H), 6.82 (t, J = 7.4 Hz,1H), 3.22 (s,
1
3
C H13ClNOS 266.0401; found: 266.0404.
13
3
1
4
1
1
H), 2.38 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ = 143.6,
3
40.1, 133.2, 132.4, 130.5, 129.6, 128.5, 126.4, 122.0, 121.9,
5.7, 18.8 (ppm). IR (KBr): ν = 3014, 2970, 2926, 2360, 1900,
571, 1486, 1405, 1315, 1266, 1210, 1118, 1092, 1050, 1030,
N-(3-Chlorophenyl)-S-methyl-S-phenylsulfoximine (3ah): White
solid (67.4 mg, 85%), m.p. 57 - 58 °C. 1H NMR (400 MHz,
CDCl ): δ = 7.88 (d, J = 7.5 Hz, 2H), 7.52 (d, J = 7.0 Hz, 1H),
3
-
1
011, 960, 748, 691, 640, 538 (cm ). MS (ESI): m/z = 245.0
7.46 (t, J = 7.1 Hz, 2H), 6.97-6.90 (m, 2H), 6.80 (d, J = 8.0 Hz,
+
13
(100), 167.0, 140.0, 104.0. HRMS (ESI-TOF) m/z: [M+H]
1H), 6.76 (d, J = 7.9 Hz, 1H), 3.16 (s, 3H) (ppm). C NMR (100
Calcd for C H NOS 246.0947; found. 246.0951.
MHz, CDCl ): δ = 146.6, 139.0, 134.4, 133.6, 130.0, 129.8,
14
16
3
1
28.6, 123.4, 121.8, 121.4, 46.2 (ppm). IR (KBr): ν = 3061,
N-(4-Methylphenyl)-S-methyl-S-phenyl Sulfoximine. (3ac): White
solid (66.2 mg, 90%), m.p. 108 - 109 °C. H NMR (400 MHz,
1
3021, 2926, 1640, 1589, 1474, 1318, 1275, 1192, 1094, 1029,
7
(100), 124.0, 77.0. HRMS (ESI-TOF) m/z: [M+H] Calcd for
C H13ClNOS 266.0401; found: 266.0404
13
-1
85, 685, 522 (cm ). MS (ESI): m/z (%) = 265.0, 202.0, 167.0
+
CDCl ): δ = 7.97 (d, J = 7.3 Hz, 2H),7.58 (t, J = 7.2 Hz, 1H),
3
7
.51 (t, J = 7.3 Hz, 2H), 6.92 (s, 4H), 3.22 (s, 3H), 2.20 (s, 3H)
13
(ppm). C NMR (100 MHz, CDCl ): δ = 142.3, 139.7, 133.2,
3
1
31.2, 129.7, 129.6, 128.8, 123.3, 46.0, 20.8 (ppm). IR (KBr): ν

6
Tetrahedron
+
N-(4-Chlorophenyl)-S-methyl-S-phenyl
Sul
A
fo
C
xim
C
in
E
e
PT
(
E
3a
D
i): MA(E
N
SI
U
-T
S
OF
C
)
R
m/
I
z: [M+H] Calcd for C H N OS 257.0743; found:
14 13 2
P
T
1
White solid (69.1 mg, 87%), m.p. 82 - 83 °C. H NMR (400
257.0746.
MHz, CDCl ): δ = 7.92 (d, J = 7.7 Hz, 2H), 7.60-7.54 (m, 1H),
3
N-4-(Trifluoromethylphenyl)-S-methyl-S-phenylsulfoximine(3ao):
7
.51 (t, J = 7.4 Hz, 2H), 7.04 (d, J = 8.3 Hz, 2H), 6.92 (d, J = 8.3
1
13
Brownish thick oil (73.6 mg, 82%). H NMR (400 MHz, CDCl
3
):
Hz, 2H), 3.22 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ =
3
δ = 7.96 (d, J = 7.3 Hz, 2H), 7.62(t, J = 7.4 Hz, 1H), 7.55 (t, J =
1
43.8, 138.9, 133.5, 129.7, 129.0, 128.6, 126.7, 124.5, 46.1
7
3
.6 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H),7.05 (d, J = 8.4 Hz, 2H),
(ppm). IR (KBr): ν = 3062, 3016, 2963, 2925, 2064, 1890, 1641,
13
.27 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ = 148.8,
3
1
6
2
585, 1484, 1444, 1293, 1258, 1193, 1092, 1023, 869, 808, 737,
-1
138.9, 133.8, 129.9, 128.6, 126.3 (JC-F = 3.7 Hz), 124.5(JC-F =
83, 652, 620, 541 (cm ). MS (ESI): m/z (%) = 266.0 (100),
19
+
311.9 Hz), 123.6 (JC-F = 10.2 Hz), 122.9, 46.4 (ppm). F NMR
370 MHz, CDCl ): δ = -61.7 (ppm). IR (KBr): ν = 3029, 2964,
18.1, 126.0, 118.1. HRMS (ESI-TOF) m/z: [M+H] Calcd for
(
3
C H ClNOS 266.0401; found:266.0412.
13
13
2
928, 2360, 1901, 1613, 1574, 1514, 1485, 1326, 1269, 1203,
-1
N-(2-Bromophenyl)-S-methyl-S-phenylsulfoximine (3aj): Light
1096, 1036, 1020, 999, 956, 826, 749, 635, 531 (cm ). MS (ESI):
m/z (%) = 299.0 (100), 154.0, 145.0, 124.0. HRMS (ESI-TOF)
m/z: [M+H] Calcd for C H F NOS 300.0664; found.
1
brown solid (69.5 mg, 75%), m.p. 64 - 65 °C. H NMR (400
+
MHz, CDCl ): δ = 8.08 (d, J = 7.7 Hz, 2H), 7.63-7.58 (m, 1H),
3
14 13 3
7
1
.58-7.49 (m, 3H), 7.20 (d, J = 7.9 Hz, 1H), 7.03 (t, J = 7.6 Hz,
H), 6.76 (t, J = 7.5 Hz, 1H), 3.25 (s, 3H) (ppm). C NMR (100
300.0656.
13
N-(2-Naphthyl)-S-methyl-S-phenylsulfoximine (3ap): Yellow
solid (74.1 mg, 88%), m.p. 91 - 92 °C. H NMR (400 MHz,
MHz, CDCl ): δ = 143.6, 139.2, 133.6, 133.1, 129.7, 128.7,
1
3
1
2
2
28.0, 123.7, 123.2, 119.5, 45.6 (ppm). IR (KBr): ν = 3011,
-1
CDCl ): δ = 7.91 (d, J = 7.5 Hz, 2H), 7.58 (d, J =8.1 Hz, 1H),
3
920, 1577, 1197, 1124, 684 (cm ). MS (ESI): m/z (%) = 310.1,
+
7.54 (d, J = 8.8 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.44 (d, J = 6.7
Hz, 1H), 7.40 (t, J = 7.1 Hz, 2H), 7.31 (s, 1H), 7.24 (t, J =7.4 Hz,
15.1, 167.0 (100), 124.0, 77.0. HRMS (ESI-TOF) m/z: [M+H]
Calcd for C H BrNOS 309.9896; found. 309.9890.
13
13
13
1
H), 7.16 (t, J = 7.2 Hz, 2H), 3.19 (s, 3H) (ppm). C NMR(100
N-(3-Bromophenyl)-S-methyl-S-phenylsulfoximine (3ak): White
solid (65.2 mg, 82%), m.p. 85 - 86 °C. H NMR (400 MHz,
MHz, CDCl ): δ = 143.0, 139.3, 134.5, 133.4, 129.64, 129.57,
128.8, 128.7, 127.5, 126.9, 126.0, 124.9, 123.8, 118.7, 46.1
3
1
CDCl ): δ = 7.95 (d, J = 7.5 Hz, 2H), 7.62-7.57 (m, 1H), 7.53 (t,
(ppm). IR (KBr): ν = 3014, 2963, 2918, 2852, 1622, 1588, 1456,
3
-
1
J = 7.3 Hz, 2H), 7.18 (s, 1H), 7.01 - 6.90 (m, 3H), 3.23 (s, 3H)
1266, 1195, 1093, 973, 743, 688, 512 (cm ). MS (ESI): m/z (%)
= 281.1 (100), 218.1, 141.1, 124.1, 77.1. HRMS (ESI-TOF) m/z:
13
(
ppm). C NMR (100 MHz, CDCl ): δ = 146.7, 139.0, 133.6,
3
+
1
30.2, 129.7, 128.6, 126.3, 124.7, 122.6, 121.8, 46.2 (ppm). IR
[M+H] Calcd for C H NOS 282.0947; found. 282.0950.
17
16
(
KBr): ν = 3156, 2917, 1637, 1486, 1359, 1306, 1115, 964, 896,
-
1
N,S-Diphenyl Sulfonamide (5aa):White solid (90.9 mg, 78%),
1
6
7
3
17, 444 (cm ). MS (ESI): m/z (%) = 310.0, 167.1 (100), 124.0,
+
m.p. 106 - 107 °C. H NMR (400MHz, CDCl
3
): δ = 7.81 (d, J =
.6 Hz, 2H), 7.57 (t, J = 7.3 Hz, 1H),7.47 (t, J = 7.5 Hz, 2H),
.29 (d, J = 8.0 Hz, 2H), 7.16 (t, J = 7.4 Hz,1H), 7.11 (d, J = 7.8
7.0. HRMS (ESI-TOF) m/z: [M+H] Calcd for C H BrNOS
13
13
7
7
09.9896; found. 309.9899.
13
N-(4-Bromophenyl)-S-phenyl-S-methyl Sulfoximine (3al): White
solid (82.5 mg, 89%), m.p. 111 - 112 °C. H NMR (400 MHz,
CDCl ): δ = 7.93 (d, J = 7.3 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H),
7
Hz, 2H), 6.81 (br, NH) (ppm). C NMR (100MHz, CDCl ): δ =
3
1
139.1, 136.4, 133.18, 129.5, 129.2, 127.3, 125.7, 122.0 (ppm). IR
(KBr): ν = 3257, 2961, 2362, 1727, 1599, 1496, 1463, 1410,
1337, 1264, 1158, 1094, 1022, 921, 803, 754, 697, 631, 599, 561
(cm-1). MS (ESI): m/z (%) = 233.0, 168.0, 141.0, 92.0, 77.0,
3
.52 (t, J = 7.6 Hz, 2H), 7.19 (d, J = 8.7 Hz, 2H), 6.87 (d, J = 8.7
13
Hz, 2H), 3.23 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ =
3
+
1
(
1
44.3, 138.9, 133.5, 132.0, 129.7, 128.7, 125.0, 114.4, 46.2
ppm). IR (KBr): ν = 3063, 3017, 2958, 2928, 2359, 1907, 1570,
483, 1318, 1289, 1206, 1095, 1023, 994, 826, 753, 631, 532
65.0. HRMS (ESI-TOF) m/z: [M+H] Calcd for C H NO S
1
2
12
2
233.0510; found: 233.0505.
-
1
N-Phenyl-S-2-methylphenyl Sulfonamide (5ba): White solid (88.9
(cm ). MS (ESI): m/z (%) = 310.0, 167.1 (100), 124.1, 90.1,
1
+
mg, 72%), m.p. 126 - 127 °C. HNMR (400 MHz, CDCl
3
): δ =
.95 (d, J = 8.2 Hz, 1H), 7.41-7.30 (m, 2H), 7.24 - 7.20 (m, 2H),
.15 (t, J = 7.6 Hz, 2H), 7.00 (d, J = 8.1 Hz,3H), 2.62 (s, 3H)
7
3
7.1. HRMS (ESI-TOF) m/z: [M+H] Calcd for C H BrNOS
13 13
7
7
09.9896; found: 309.9899.
13
N-(4-Iodophenyl)-S-methyl-S-phenyl
Sulfoximine
(3am):
(ppm). C NMR (100 MHz, CDCl ): δ = 137.44, 137.37, 136.6,
3
Yellowish solid (92.1 mg, 86%), m.p. 99 - 100 °C. 1H NMR (400
MHz, CDCl3) δ = 7.93 (d, J = 7.3 Hz, 2H), 7.60 (t, J = 7.4 Hz,
133.2, 132.7, 130.1, 129.4, 126.4, 124.9, 120.4, 20.5 (ppm). IR
(KBr): ν = 3282, 3064, 2960, 2922, 2856, 2362, 1732, 1633,
1595, 1490, 1467, 1405, 1264, 1216, 1159, 1091, 1025, 967, 915,
1
=
H), 7.53 (t, J = 7.6 Hz, 2H), 7.38 (d, J = 8.7 Hz, 2H), 6.76 (d, J
8.7 Hz, 2H), 3.23 (s, 3H) (ppm). C NMR (100 MHz, CDCl3)
13
-1
804, 755, 696, 626, 588, 540 (cm ). MS (ESI): m/z (%) = 247.0,
+
δ = 145.1, 139.0, 137.9, 133.6, 129.7, 128.7, 125.5, 84.8, 46.2
ppm). IR (KBr): ν = 3068, 3022, 3001, 2962, 2924, 2362, 1903,
182.0, 155.0, 91.0 (100), 65.0. HRMS (ESI-TOF) m/z: [M+H]
(
Calcd for C H NO S 248.0740; found: 248.0748.
13
14
2
1
9
=
576, 1481, 1444, 1400, 1319, 1288, 1201, 1093, 1037, 1018,
-1
N-Phenyl-S-4-methylphenyl Sulfonamide (5ca): White solid (92.6
97, 966, 822, 744, 687, 634, 609, 530 (cm ). MS (ESI): m/z (%)
358.0 (100), 232.1, 218.1, 157.0, 79.0. HRMS (ESI-TOF) m/z:
1
mg, 75%), m.p. 102 - 103 °C. H NMR (400 MHz, CDCl ): δ =
3
+
7.70 (d, J = 7.9 Hz, 2H), 7.41 (s, 1H),7.22 (t, J = 7.5 Hz, 4H),
[
M+H] Calcd for C H INOS 357.9757; found: 357.9773.
13
13
13
7
.11 - 7.06 (m, 3H), 2.36 (s, 3H) (ppm). C NMR (100 MHz,
N-(4-Cyanophenyl)-S-methyl-S-phenyl sulfoximine (3an): White
solid (69.1 mg, 90%), m.p. 108 - 109 °C. H NMR (400 MHz,
CDCl ): δ = 144.0, 136.7, 136.1, 129.8, 129.4, 127.4, 125.3,
121.5, 21.6 (ppm). IR (KBr): ν = 3264, 3226, 2956, 2361, 1917,
3
1
CDCl ): δ = 7.93 (d, J = 7.7 Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H),
1645, 1572, 1469, 1383, 1327, 1275, 1221, 1151, 1097, 1024,
3
-
1
7
.55 (t, J = 7.5 Hz, 2H), 7.36 (d, J = 8.1 Hz,2H), 7.00 (d, J = 8.1
921, 810, 757, 652, 603, 576, 546 (cm ). MS (ESI): m/z (%) =
247.0, 182.0, 155.0, 91.0 (100), 65.0. HRMS (ESI-TOF) m/z:
13
Hz, 2H), 3.28 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ =
3
+
1
4
1
50.3, 138.5, 133.9, 133.3, 130.0, 128.5, 123.3, 119.7, 104.1,
6.6 (ppm). IR (KBr): ν = 3055, 2963, 2921, 2555, 2221, 1595,
498, 1279, 1211, 1171, 1095, 1019, 845, 796, 749, 692, 519
[M+H] Calcd for C H NO S 248.0740; found: 248.0745.
13
14
3
N-Phenyl-S-4-fluorophenyl Sulfonamide 1 (5da): White solid
(100.4 mg, 80%), m.p. 109 - 111 °C. H NMR (400 MHz,
-
1
(cm ). MS (EI): m/z = 256.1 (100), 167.1, 125.0, 77.1. HRMS
CDCl ): δ = 7.82 (dd, J = 8.3, 3.7 Hz, 2H), 7.33 - 7.26 (m, 2H),
3
13
7
.18 - 7.07 (m, 5H) (ppm). C NMR (100 MHz, CDCl ): δ =
3

7
-
1
1
1
65.4 (JC-F = 254.0 Hz), 136.3, 135.1, 130.1(J
25.9, 122.1, 116.4 (JC-F = 22.6 Hz) (ppm). F NMR (370 MHz,
A
=
C
9
C
.4
E
Hz
P
),
T
12
E
9
D
.6, MA68
N
9,
U
64
S
0
C
, 5
R
84
I
, 527 (cm ). MS (ESI): m/z (%) = 247.0, 168.0,
P
T
C-F
19
+
141.0, 106.0 (100), 77.0, 65.0. HRMS (ESI-TOF) m/z: [M+H]
Calcd for C H NO S 248.0740; found: 248.0733.
CDCl ) δ = -104.5 (ppm). IR (KBr): ν = 3215, 3047, 2923, 2858,
3
13 14
2
2
1
797, 1912, 1592, 1494, 1464, 1408, 1337, 1302, 1231, 1154,
092, 1019, 938, 906, 841, 760, 712, 601, 543 (cm ). MS (ESI):
-1
N-(4-Methoxyphenyl)-S-phenylsulfonamide (5ae): White solid
1
(
92.8 mg, 68%), m.p. 87 - 88 °C. H NMR (400 MHz, CDCl ): δ
3
m/z (%) = 251.0, 168.0, 159.0, 95.0, 92.0 (100), 65.0. HRMS
+
= 7.71 (d, J = 7.8 Hz, 2H), 7.53 (t, J = 7.4 Hz, 1H), 7.42 (t, J =
(ESI-TOF) m/z: [M+H] Calcd for C H FNO S 252.0489;
12 11 2
7
3
.5 Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H), 6.75 (d, J = 8.3 Hz, 2H),
found: 252.0481.
13
.75 (s, 3H) ppm. C NMR (100 MHz, CDCl ): δ = 158.2, 139.1,
3
N-Phenyl-S-4-chlorophenyl Sulfonamide (5ea): White solid
133.0, 129.1, 128.8, 127.4, 125.7, 114.6, 55.5 ppm. IR (KBr): ν =
1
(113.5 mg, 85%), m.p. 103 - 105 °C. H NMR (400 MHz,
3257, 3013, 2965, 2841, 1888, 1609, 1513, 1454, 1332, 1253,
-
1
CDCl ): δ = 7.71 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H),
1159, 1095, 911, 822, 726, 630, 538 (cm ). MS (ESI): m/z =
3
+
7
.29 (d, J = 7.4 Hz, 2H), 7.17 (t, J = 7.3 Hz, 1H),7.08 (d, J = 7.9
263.0, 122.0 (100). HRMS (ESI-TOF) m/z: [M+H] Calcd for
13
Hz, 2H) (ppm). C NMR (100 MHz, CDCl ): δ = 139.8, 137.6,
C H NO S 264.0689; found: 264.0682.
3
13 14
3
1
3
1
7
1
36.1, 129.6, 129.5, 128.8, 126.0, 122.1 (ppm). IR ( KBr): =
254, 3089, 3044, 2961, 2927, 2865, 1913, 1724, 1651, 1584,
470, 1401, 1336, 1276, 1217, 1157, 1089, 1017, 925, 894, 825,
N-(4-Fluorophenyl)-S-phenyl Sulfonamide (5af): White solid
1
(102.9 mg, 82%), m.p. 110 - 111 °C. H NMR (400 MHz,
-
1
CDCl ): δ = 7.78 (d, J = 7.7 Hz, 2H), 7.53 (t, J = 7.4 Hz, 1H),
3
55, 699, 614, 545 (cm ). MS (ESI): m/z (%) = 267.0, 168.0,
+
7.43 (t, J = 7.6 Hz, 2H), 7.07 (m, 2H), 6.90 (t, J = 8.3 Hz, 2H).
11.0, 92.0 (100), 65.0. HRMS (ESI-TOF) m/z: [M+H] Calcd
13
C NMR (100 MHz, CDCl ): δ = 160.7 (J = 243.8 Hz), 138.6,
3
C-F
for C H ClNO S 268.0194; found: 268.0200.
12
11
2
1
33.3, 132.3, 129.2, 127.4, 124.7 (J = 8.3 Hz), 116.2 (JC-F
=
C-F
19
N-Phenyl-S-4-bromophenyl Sulfonamide 1 (5fa): White solid
136.8mg, 88%), m.p: 117 - 118 °C. H NMR (400 MHz,
CDCl ): δ = 7.64 (d, J = 8.2 Hz, 2H), 7.56 (d, J = 8.0Hz, 2H),
22.7 Hz) ppm. F NMR (370 MHz, CDCl ): δ = -116.2 (ppm).
3
(
IR (KBr): = 3259, 3066, 2933, 2862, 1618, 1520, 1466, 1448,
1400, 1327, 1294, 1234, 1163, 1117, 1091, 1070, 1016, 922, 841,
3
-
1
7
3
1
3
1
7
1
.25 (t, J = 7.5 Hz, 2H), 7.14 (d, J = 7.4 Hz, 1H), 7.12 - 7.06 (m,
754, 733, 687, 655, 586, 561 (cm ). MS (ESI): m/z (%) = 251.0,
168.0, 141.0, 110.0, 91.0 (100), 77.0, 65.0. HRMS (ESI-TOF)
13
H) (ppm). C NMR (100 MHz, CDCl ): δ = 138.1, 136.1,
3
+
32.5, 129.6, 128.9, 128.2, 126.0, 122.1 (ppm). IR (KBr): ν=
253, 3087, 2925, 2865, 2804, 2362, 1912, 1726, 1647, 1570,
468, 1401, 1336, 1275, 1217, 1157, 1071, 1008, 925, 894, 821,
m/z: [M+H] Calcd for C H FNO S 252.0489; found.
12
11
2
252.0495.
-
1
N-(4-Chlorophenyl)-S-phenyl Sulfonamide (5ai): White solid
48, 697, 605, 544 (cm ). MS (ESI): m/z (%) = 312.0, 168.1,
1
+
(100.5 mg, 75%), m.p. 120 - 122 °C. H NMR (400 MHz,
55.0, 92.1 (100), 65.1. HRMS (ESI-TOF) m/z: [M+H] Calcd
CDCl ): δ = 7.78 (d, J = 7.7 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H),
3
for C H BrNO S 311.9688; found: 311.9695.
12
11
2
7
.45 (t, J = 7.6 Hz, 2H), 7.19 (d, J = 8.5 Hz, 2H), 7.03 (d, J = 8.5
13
N-Phenyl-S-4-trifluoromethylphenyl Sulfonamide (5ga): White
solid (118.9 mg, 79%), m.p. 121 - 123 °C. H NMR (400 MHz,
CDCl ): δ = 7.89 (d, J = 8.1 Hz, 2H), 7.70 (d, J = 8.1 Hz, 2H),
7
Hz, 2H) (ppm). C NMR (100 MHz, CDCl ): δ = 138.8, 135.2,
3
1
133.4, 131.2, 129.6, 129.3, 127.3, 123.2 (ppm). IR ( KBr): ν =
3257, 3101, 3068, 2964, 2926, 2852, 1896, 1597, 1491, 1448,
1390, 1329, 1292, 1225, 1161, 1090, 1014, 916, 825, 754, 727,
3
.27 (t, J = 7.6 Hz, 2H), 7.16 (t, J = 7.3 Hz,1H), 7.09 (d, J = 7.7
13
-1
Hz, 2H) (ppm). C NMR (100 MHz, CDCl ): δ = 142.7, 135.9,
631, 565, 688, 586, 505 (cm ). MS (ESI): m/z (%) = 267.0,
3
1
1
34.8 (JC-F = 33.0 Hz), 129.7, 127.9, 126.3 (J = 3.6Hz), 126.2,
23.3 (JC-F = 271.4 Hz), 122.2 (ppm). F NMR (370 MHz,
168.0, 141.0, 126.0, 91.0 (100), 77.0, 65.0. HRMS (ESI-TOF)
C-F
19
+
m/z: [M+H] Calcd for C H ClNO S 268.0194; found.
12
11
2
CDCl ) δ = -63.2 (ppm). IR (KBr): ν = 3107, 3056, 2960, 2923,
268.0186.
3
2
1
873, 2808, 1934, 1593, 1493, 1470, 1404, 1332, 1329, 1165,
128, 1107, 1092, 1064, 1016, 899, 845, 798, 717, 694, 606, 544
N-(4-Bromophenyl)-S-phenyl Sulfonamide (5al): White solid
(108.9 mg, 70%), m.p. 132 - 134 °C. H NMR (400 MHz,
1
-
1
(cm ). MS (ESI): m/z (%) = 301.0, 236.0, 218.0, 145.0,
+
CDCl
3
): δ = 7.77 (d, J = 7.5 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H),
9
2.1(100), 65.1. HRMS (ESI-TOF) m/z: [M+H] Calcd for
7
.45 (t, J = 7.7 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 6.97 (d, J = 7.1
C H F NO S 302.0457; found. 302.0451.
13
13
11
3
2
Hz, 2H) (ppm). C NMR (100 MHz, CDCl ): δ = 138.9, 135.7,
3
N-(o-Tolyl)-S-phenyl Sulfonamide (5ab): White solid (88.9 mg,
133.4, 132.5, 129.3, 127.3, 123.5, 118.9 (ppm). IR (KBr): ν =
3234, 3089, 3068, 2922, 2848, 1905, 1587, 1489, 1448, 1389,
1325, 1292, 1221, 1159, 1092, 1072, 1012, 914, 810, 727, 688,
1
7
2%), m.p. 121 - 123 °C. H NMR (400 MHz, CDCl ): δ = 7.73
3
(d, J = 7.9 Hz, 2H), 7.55 (t, J = 7.5 Hz,1H), 7.43 (t, J = 7.7 Hz,
-
1
2
4
H), 7.30 (d, J = 7.8 Hz, 1H), 7.17 - 7.11 (m, 1H), 7.08 (d, J =
.4 Hz, 2H), 6.42 (br, NH), 1.98 (s, 3H) (ppm). C NMR (100
561, 501 (cm ). MS (ESI): m/z (%) = 312.0, 168.0, 141.0, 171.0,
13
+
91.0 (100), 77.0, 65.0. HRMS (ESI-TOF) m/z: [M+H] Calcd for
MHz, CDCl ): δ = 139.8, 134.5, 133.1, 131.7, 130.9, 129.1,
C H BrNO S 311.9688; found. 311.9681.
3
12 11
2
1
3
1
27.3, 127.1, 126.6, 124.7, 17.6 (ppm). IR (KBr): ν = 3359,
N-(4-cyanophenyl)-S-phenyl Sulfonamide (5an): Yellow solid
224, 3062, 2922, 2361, 1908, 1638, 1449, 1406, 1328, 1256,
1
-
1
(92.9 mg, 72%), m.p. 148 - 149 °C. H NMR (400 MHz, CDCl ):
3
153, 1092, 962, 909, 790, 755, 687, 594, 543 (cm ). MS (ESI):
δ = 7.86 (d, J = 7.8 Hz, 2H), 7.60 (t, J = 7.3 Hz, 1H), 7.54 - 7.48
m/z (%) = 247.0, 168.0, 141.0, 106.0 (100), 77.0, 65.0. HRMS
13
+
(m, 4H), 7.19 (d, J = 8.0 Hz, 2H) (ppm). C NMR (100 MHz,
(ESI-TOF) m/z: [M+H] Calcd for C H NO S 248.0740; found:
13 14 2
CDCl ): δ = 141.0, 138.7, 133.9, 133.8, 129.6, 127.3, 119.6,
3
2
48.0764.
1
18.5, 108.1 (ppm). IR (KBr): ν = 3253, 2964, 2221, 1610, 1508,
-1
N-(p-Tolyl)-S-phenyl Sulfonamide(5ac): White solid (93.9 mg,
7
1332, 1159, 1092, 922, 812, 585 (cm ). MS (ESI): m/z = 258.0,
141.0, 77.0 (100). HRMS (ESI-TOF) m/z: [M+H] Calcd for
1
+
6%), m.p. 118 - 120 °C. H NMR (400 MHz, CDCl ): δ = 7.74
3
(d, J = 7.9 Hz, 2H), 7.53 (t, J = 7.2 Hz, 1H), 7.43 (t, J = 7.6 Hz,
C H N O S 259.0536; found. 259.0542.
13
11
2
2
2
H), 7.03 (d, J = 8.0 Hz, 2H), 6.94 (d, J = 8.0 Hz, 2H), 6.53 (br,
13
N-(2-Naphthyl)-S-phenyl Sulfonamide (5ap): White solid (111.8
NH), 2.27 (s, 3H) (ppm). C NMR (100 MHz, CDCl ): δ =
1
3
mg, 79%), m.p. 97 - 98 °C. H NMR (400 MHz, CDCl ): δ =
3
1
(
1
39.2, 135.8, 133.7, 133.0, 130.0, 129.1, 127.4, 122.8, 21.0
ppm). IR (KBr): ν = 3435, 3244, 2923, 2362, 1629, 1512, 1449,
389, 1327, 1266, 1221, 1161, 1092, 1027, 914, 812, 757, 726,
7
.83 (d, J = 7.8 Hz, 2H), 7.78 - 7.67 (m,3H), 7.55 (s, 1H), 7.50
(
d, J = 7.6 Hz, 1H), 7.47 - 7.36 (m, 4H), 7.24 (d, J = 8.8 Hz, 1H)
13
(ppm). C NMR (100 MHz, CDCl ): δ = 139.1, 134.0, 133.7,
3

8
Tetrahedron
Ghazanfarpour-Darjani, M.; Talei Bavil Olyai, M. R.; Shamami, S. F. J.
1
33.2, 131.3, 129.5, 129.2, 127.8, 127.7, 12
A
7.4
C
,
C
12
E
6.
P
8,
TED
12
5
.7, MANUSCRIPT
Sulfur Chem. 2016, 37, 211-221.
1
1
7
1
21.3, 118.8 (ppm). IR (KBr): ν = 3261, 3057, 2923, 1633, 1600,
514, 1446, 1416, 1354, 1308, 1157, 1092, 968, 928, 858, 814,
52, 729, 687, 646, 575, 525 (cm ). MS (ESI): m/z (%) = 283.0,
68.0, 142.0 (100), 115.0, 91.0, 77.0, 65.0. HRMS (ESI-TOF)
1
0. (a) Kantam, M. L.; Neelima, B.; Reddy, C. V.; Neeraja, V. J. Mol. Catal.
A: Chem. 2006, 249, 201-206. (b) Islam, S. M.; Mondal, S.; Mondal, P.;
Roy, A. S.; Tuhina, K.; Mobarok, M. Inorg. Chem. Commun. 2011, 14,
1352-1357. (c) Nasrollahzadeh, M.; Ehsani, A.; Maham, M. Synlett
2014, 25, 505-508. (d) Nasrollahzadeh, M.; Rostami-Vartooni, A.;
Ehsani, A.; Moghadam, M. J. Mol. Catal. A: Chem. 2014, 387, 123-129.
1. Pan, C.; Cheng, J.; Wu, H.; Ding, J.; Liu, M. Synth. Commun. 2009, 39,
-
1
+
m/z: [M+H] Calcd for C H NO S 284.0740; found. 284.0747.
16
14
2
1
1
Acknowledgments
2
082-2092.
2. Shekhar, S.; Dunn, T. B.; Kotecki, B. J.; Montavon, D. K.; Cullen, S. C.
We are grateful to the Natural Science Foundation of Hunan
Province (No. 2017JJ3027), the Fundamental Research Funds for
Hunan University (No. 531107040840).
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