Intermolecular sulfenoamination of alkenes with sulfonamides and: N -sulfanylsuccinimides to access β-sulfonylamino sulfides and dihydrobenzothiazines

Article abstract of DOI:10.1039/c7ob01225j

An acid-catalyzed intermolecular sulfenoamination reaction of alkenes is developed with sulfonamides as the nitrogen source and N-sulfanylsuccinimides as the sulfur source. This methodology provides a straightforward and general way to synthesize various β-sulfonylamino sulfides with high regio- and diastereoselectivity. The developed method was coupled with intramolecular C-N coupling in a one-pot procedure to afford a series of dihydrobenzothiazine derivatives, a kind of important heterocycle used as biologically active compounds in medicinal chemistry.

Full text of DOI:10.1039/c7ob01225j

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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DOI: 10.1039/C7OB01225J
Journal Name
ARTICLE
Intermolecular sulfenoamination of alkenes with sulfonamides
and N‐sulfanylsuccinimides to access ‐sulfonylamino sulfides and
dihydrobenzothiazines
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
a
a
a
a
a
Tao Liu, Jun Tian, Wen‐Chao Gao,* Hong‐Hong Chang, Qiang Liu,* Xing Li, and Wen‐Long Wei
DOI: 10.1039/x0xx00000x
An acid‐catalyzed intermolecular sulfenoamination reaction of alkenes is developed with sulfonamides as nitrogen source
and N‐sulfanylsuccinimides as sulfur source. This methodology provides a straightforward and general way to synthesize
various ‐sulfonylamino sulfides with high regio‐ and diastereoselectivity. The developed method was coupled with
intramolecular C‐N coupling in a one‐pot procedure to afford a series of dihydrobenzothiazine derivatives, one kind of
important heterocycles as biologically active compounds in medicinal chemistry.
www.rsc.org/
Sulfenoamination reaction of alkenes directly couples two
common groups, sulfenyl group and amino group to C‐C double
bond, which is abundant and readily available in nature, and is
Introduction

‐Amino sulfides are important building blocks in organic
one of the most useful tools to construct ‐amino sulfides.
synthesis, and have been widely used in synthetic chemistry as
well as modern pharmaceutical industry (Figure 1). For example,
these scaffolds exist in commercially approved drugs including
Specifically, several methods for the intramolecular
sulfenoamination using N‐alkenyl sulfonamides as substrates
have been well investigated to prepare N‐heterocyclic sulfides.
Denmark and Shi groups separately reported the
enantioselective intramolecular reaction of N‐alkenyl
sulfonamides with electrophilic sulfenyl reagent methyl
Amoxicillin (a
‐lactam‐based antibiotic) and Viracept (an
1
a
antiretroviral drug), in bioactive non‐natural compounds like
K
ATP channel openers (embedding a dihydrobenzothiazine core)
and in some N‐S bidentate ligands for transition metal
1b
benzenesulfenate (MeOSPh) or phenylthiophthalimide
catalysis.1c
2
(
PhthSPh). Most recently, Wirth and coworkers also described
OH
PhS
HN
an
efficient
and
enantioselective
intramolecular
OH
N
sulfenoamination of N‐alkenyl sulfonamides mediated by
iodine(III) reagents with sulfur nucleophiles (Scheme 1a).3
However, compared with intramolecular process,
H
H
H
O
O
N
S
H N
2
Me
(
a) Intramolecular sulfenoamination
O
N
R
SPh
NTs
O
OH
NHtBu
PhthSPh or PhSOMe
TsN
TsHN
OH
Chiral catalyst
or
Amoxicillin
O
Viracept
R
R
CH2Cl2, 0 oC or 35-70 o
C
H
N
SPh
Ph
Ph
PhSNa
Chiral iodine (III) reagent
(stoichiometric amount)
NHTs
Ts
N
R
PhO
PhO
SPh
P
N
S
Tol
S
Bn
CH Cl , rt
2
2
KATP-Channel Openers
N,S-bidentate ligand
‐amino sulfides
(b) Intermolecular acetamidosulfenylation
PhSH
Figure 1. Useful structures containing

O
3
R CN (excess amount)
NH
R1
SPh
R2
R1
I2 or iodide (cat.)
Oxidant, 80-100 o
R3
R2
C
(
c) This work: direct intermolecular sulfenoamination with
a.
sulfonylamides as N-source
College of Chemistry and Chemical Engineering, Taiyuan University of Technology,
Taiyuan 030024, P. R. China
gaowenchao@tyut.edu.cn; liuqiang@tyut.edu.cn
College of Date Science, Taiyuan University of Technology, Taiyuan 030024, P. R.
China
N-sulfanylsuccinimides
Ts
N
R1
TsNH2 (1.1 eq)
Acid (cat.)
TsHN
R1
R2
SR
b.
Cu (1.1 eq)
DMF, 120 o
R3
CH2Cl2, rt
R1
R2
C
R2
S
†
Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [Conditions optimization for
the synthesis of 11a, Mass Spectrometry for mechanism study, Copies of NMR and
Scheme 1. Different methods for sulfenoamination of alkenes
IR spectra for all new compounds; X‐ray crystal data for 4m and
9 (CIF)]. See
DOI: 10.1039/x0xx00000x
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Journal Name
which are kinetically and thermodynamically favoured, the than other solvents (entries 9‐14), and no desiredVpiewroAdrtuiccletOwnlianes
detected when the reaction was perform
EtOAc (entries 11, 12 and 14). Moreover, we also tested three
sulfenylating reagents such as p‐tolylthiophthalimide ( ), p‐
tolylthio chloride ( ), and methyl p‐tolylsulfenate ( ), that were
previously used for intramolecular sulfenoamination of olefins,
while none of them could give better results than 2a (entries 15‐
D
e
O
d
I:
i
1
n
0.
M
10
e
39
C
/
N
C
,
7O
T
B
H
0
F
12
a
2
n
5
d
J
development of catalytic intermolecular sulfenoamination is
more challenging and highly desirable. To realize an
4
5
intermolecular sulfenoamination of alkenes, an alternative
6
7
5
option was assisted with nitriles as solvent and N‐nucleophiles,
2
and successful examples on the synthesis of
‐acetamino
sulfides have been disclosed using nitrile as nitrogen source and
1
7). For example, 5 had weak reactivity for the intermolecular
thiol as sulfur source through a Ritter‐type reaction (Scheme
sulfenoamination, and 4a was only obtained in 41% yield even
the reaction was stirred for 24 h (entry 15); as for sulfenylating
6
1
b). In addition, the electrophilic fluorinating agents N‐
7
a,b
fluorobenzenesulfonimide (NFSI),
could also serve as reagents
nitrogen source for intermolecular sulfenoamination under low yield, while the corresponding
copper catalysis. However, direct
6
and
7
,

‐sulfonylamino sulfide 4a was produced in
‐chloro sulfide or
intermolecular methoxyl sulfide was isolated as a major product (entries 16 and

‐
sulfenoamination of alkenes using simple sulfonamides as 17).
nitrogen source, to the best of our knowledge, has been
scarcely explored.
Table 1. Evaluation of reaction conditionsa
N‐Sulfanylsuccinimides, bench stable and readily accessible
reagents, have been widely used to introduce sulfenyl groups to
8
various molecules. For example, our group have recently
developed an efficient method for the synthesis of 3‐
sulfenylated coumarins through the electrophilic cyclization of
9
a
Entry
R‐S‐Tol
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
5
Cat. (10 mol %)
0
Solvent
Yield (%)b
alkynoates with N‐sulfanylsuccinimides as sulfur sources. Fu
and coworkers reported the isothiocyanatophenylthiation and
azidoarylthiation of alkenes using the combination of N‐
sulfanylsuccinimides and superstoichiometric amount of
1
2
3
4
5
6
7
8
9
CH
CH
CH
CH
CH
CH
CH
2
2
2
2
2
2
2
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2
2
2
2
2
2
2
2
0
TfOH (10)
TfOH (20)
MsOH (20)
70
74
80
trace
trace
20
84
73
76
0
1
0
trimethylsilyl derivatives (TMSNCS or TMSN
3
). Although ‐
sulfonamino sulfides could be accessed through ring‐opening of
1
1
N‐tosylaziridines with sulfur nucleophiles, the preparation of
N‐tosylaziridines and the lower stereoselectivity of nucleophilc
H
3
PO
TFA (20)
FeCl (20)
BF •Et O (20)
4
(20)
11a‐c
substitution often made these methods not practicable.
Considering the availability, the safety and enviromental issues
of nitrogen source, the direct, stereoselective sulfenoamination
3
of alkene to access
‐amino sulfides using stoichiometric
amount of sulfonamides and N‐sulfanylsuccinimides is more
CH Cl
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
attractive and highly warranted. In continuation of our research
BF
BF
BF
BF
BF
BF
BF
BF
BF
•Et
•Et
•Et
•Et
•Et
•Et
•Et
•Et
•Et
O (20)
O (20)
O (20)
O (20)
O (20)
O (20)
O (20)
O (20)
O (20)
DCE
9
work on C‐heteroatom bond formation, we herein report an
acid‐catalyzed regio‐ and stereoselective intermolecular
sulfenoamination for the synthesis of ‐sulfonylamino sulfides
10
11
12
13
14
CHCl
3
MeCN
THF
using simple alkenes, stoichiometric amount of sulfonamides
and N‐sulfanylsuccinimides as starting materials, and a new
strategy for the synthesis of dihydrobenzothiazine derivatives
has also be developed through this intermolecular
sulfenoamination reaction coupled with copper‐mediated
intramolecular C‐N coupling in a one‐pot procedure (Scheme
0
Toluene
EtOAc
70
0
15c
CH
CH
CH
41
21
0
1
c).
2
Cl
2
Cl
2
Cl
2
2
2
1
6d
6
Results and discussion
7e
1
7
Initially, styrene (1a), N‐(p‐tolylthio)succinimide (2a), and p‐
toluenesulfonamide (3a) were used as model substrates to
investigate the intermolecular sulfenoamination reaction (Table
Me
O
S
Cl
Me
SOMe
N
S
1
). To our delight, p‐toluenesulfonamide could serve as nitrogen
Me
source in 1.1 equivalent amount for the sulfenoamination of
styrene in the presence of catalytic amount of Brønsted or Lewis
acid (entries 1‐8), and the desired product 4a was
O
5
6
7
a
Reaction conditions: 1a (0.3 mmol), 2a (0.45 mmol), 3a (0.33 mmol), catalyst(10
regioselectively produced in 84% yield when BF
as the catalyst (entry 8). Further evaluation on reaction solvents
showed that CH Cl was more suitable for this transformation
3 2
∙Et O was used
(1 mL), at room temperature for 4‐8 h. b Isolated yields. Reaction
c
mol %), in CH
2
Cl
2
time: 24 h. d (2‐Chloro‐2‐phenylethyl)(p‐tolyl)sulfane was isolated in 41% yield.
e
2
2
(
2‐Methoxy‐2‐phenylethyl)(p‐tolyl)sulfane was isolated in 67% yield.
2
| J. Name., 2012, 00, 1‐3
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Next, our efforts focused on exploring the scope and deficient nature, ‐unsaturated carbonyl compounds are
View Article Online
DOI: 10.1039/C7OB01225J
intermolecular particularly challenging substrates for difunctionalization
limitation
of
the
regioselective
sulfenoamination reaction. As shown in Table 2, a variety of reactions. Nevertheless, the sulfenoamination reactions using
styrene derivatives with different functional groups were firstly chalcones bearing either electron‐rich or ‐poor groups on
subjected to the optimal reaction conditions (Table 1, entry 6). different aryl moieties also proceeded well, and delivered the
In general, various functional groups on the aryl ring of alkenes corresponding
are well‐tolerated, including p‐methyl, p‐ or o‐chloro, and p‐ or reactivity and diastereoselectivity. The exact structure and
m‐bromo groups 4b ). 2‐Vinylnaphthalene was also stereoselectivity of 4n was unambiguously confirmed by its X‐
compatible with this transformation, and 4g was afforded in 66% ray crystallography. The ‐unsaturated ester 1o was also
‐sulfenyl‐‐sulfonamido ketones 4j‐n with high
(
‐f
,
yield. In addition to terminal alkenes, several substrates bearing tested for this reaction, and gave the product 4o with high yield
internal C‐C double bond were also examined for the present and diastereoselectivity. The practicality of such process was
transformation, affording the corresponding
sulfides in good to excellent yields. For example, trans‐stillbene loading (5 mol % of BF
gave the corresponding stereospecific product 4h in 76% yield; produce 2.13 g of 4j in 85% yield with no significant loss of
as for trans‐ ‐methyl styrene, the desired product 4i was efficiency. As for the aliphatic alkenes, both the regio‐ and
obtained in 94% yield with lower diasteroslectivity. Due to their stereoselectivity of sulfenoamination reaction were tested

‐sulfonylamido also tested for a gram‐scale synthesis of 4j with a lower catalyst
3
∙Et O). To our delight, the reaction could
2

electron‐
using different substrates: the sulfenoamination reaction of
linear 1‐octene (1p) displayed poor regioselectivity, and gave a
Table 2. Screening of alkenes for sulfenoamination reactiona
mixed
‐sulfonamido sulfides 4pa and 4pb in 77% yield;
cyclohexene was a good substrate for this transformation, and
the desired product 4q was diastereoselectively obtained in 73%
yield. Furthermore, for the complex olefin substrates, excellent
regioselectivities were also observed. For example, the
regioselective product 4r with a steroid skeleton could be
obtained in 70% yield, and even for the molecule with two C‐C
double bonds such as (S)‐(+)‐Carvone, the sulfenoamination
only regioselectively occurred at the terminal position,
delivering the desired product 4s in 85% yield, but with lower
diastereoselectivity. Additionally, the present transformation
was also suitable for intramolecular sulfenoamination reaction,
and both
kinetically favoured sulfenyl pyrrolidines
yields (for the X‐ray structure of , see Supporting Information).

‐tosylamido and
‐tosylamido alkenes gave the
8
and in excellent
9
9
Table 3. Screening of N‐sulfanylsuccinimides and amides for the intermolecular
sulfenoamination reactiona
NHSO R2
2
O
BF •Et O (20 mol %)
2
3
2
SR1
Ph
+
O
N
+ R SO NH
2
2
R1
CH Cl , rt
2
2
SR1
1a
2
3
4
NHTs
S
NHTs
NHTs
SPh
S
Ph
Ph
Ph
OMe 4v, 16 h, 90%b
4
t, 6 h, 91%
NHTs
S
4u, 16 h, 90%
Cl
Br
NHTs
NHTs
S
S
Ph
Ph
Ph
w, 18 h, 73%c
4x, 5 h, 67%d
4y, 18 h, 67%
4
NHBs
S
NHNs
NHMs
S
S
Ph
Ph
Ph
a
Typical conditions: 1 (0.3 mmol), 2a (0.45 mmol), 3a (0.33 mmol), BF
3
∙Et
2
O (0.06
Me
aa, 12 h, 71%c
Me
Me
z, 10 h, 80%
4
4bb, 8 h, 83%
4
mmol), in CH
of BF
2
Cl
2
(1.0 mL), at room temperature. b TfOH (0.03 mmol) was instead
c
d
3
∙Et
2
O. TfOH (0.06 mmol) was instead of BF
3
∙Et
2
O. The ratio of two isomers
a
Typical conditions: 1a (0.3 mmol), 2 (0.45 mmol), 3 (0.33 mmol), BF
3
∙Et
2
O (0.06
O (0.12 mmol) was used.
O. TfOH (0.03 mmol) was instead of
1
e
was determined by H NMR. The reaction was performed with 1 (5 mmol), 2a (7.5
mmol), 3a (0.25 mmol) in CH
mmol) was used.
b
mmol), in CH
2
Cl
2
(1.0 mL), at room temperature. BF
3
∙Et
2
f
2
Cl
2
(20 mL), at room temperature. BF
3
∙Et
2
O (0.12
c
d
TfOH (0.06 mmol) was instead of BF
∙Et O.
3
∙Et
2
BF
3
2
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Furthermore, a series of N‐sulfanylsuccinimides and amides excellent yields. Methanesulfonamide was also suiVtieawbAlerticfloerOtnhlinies
were also examined in the present reaction system (Table 3). one‐pot two‐step reaction, and gave the dDeOsI:ir1e0d.10p3r9o/Cd7uOcBt01112f25inJ
Likewise, substitutions on the thiophenol moiety, including 69% yield. Moreover, with cyclohexene as a substrate, the
electron‐rich and ‐poor groups did not affect the reaction dihydrobenzothiazine 11g could be stereoselectively
efficiency, and the desired products 4t
moderate to excellent yields. Even if N‐sulfanylsuccinimide was
‐
x
were produced in synthesized in 65% yield.
To gain insight into the mechanism of presented
derived from aliphatic ethanethiol, the sulfenoamination intermolecular sulfenoamination reaction, several control
reaction of styrene could also afford 4y in 67% yield. Apart from experiments were performed as shown in Scheme 2. First, when
p‐toluenesulfonamide,
benzenesulfonamide,
other
sulfonamides,
including chalcone 1j was treated with N‐(p‐tolylthio)succinimide 2a
and under standard conditions for 1 h in the absence of TsNH , a
p‐nitrobenzenesulfonamide
2
methanesulfonamide, were all suitable substrates, which could sulfur‐containing intermediate (331.24) was detected in mass
transform to the corresponding products 4z 4aa and 4bb in spectroscopy (for details, see Supplementary Information); the
good yields. However, this protocol also suffered the limitation addition of TsNH (1.1 equiv) to this mixture could also
,
2
of amino sources, and the attempts with acetoamide, stereoselectively gave the desired product in 75% yield. These
succinimide or benzylamine as amino source failed to give any experiments indicated that the thiiranium ion, which contained
13
desired product.
As one of the most important heterocycles, dihydro‐2H‐ involved
benzo[b][1,4]thiazine and their derivatives exhibit a broad stereoselectively converted to products by the nucleophilic
a three‐membered episulfonium structure, was possibly
in the sulfenoamination reaction, and
1
2
spectrum of bio‐ and pharmacological activities. After the attack of sulfonamides.
efficient and regioselective synthesis of various ‐sulfonylamino
sulfides containing ‐aryl group, we envisaged that
dihydrobenzothiazines could be accessed using



‐
sulfonylamino sulfides through intramolecular C‐N coupling. To
our delight, after condition optimization (for details, see
Supporting Information), the preparation of 3‐aryl dihydro‐2H‐
benzo[b][1,4]thiazines could be realized with the use of simple
alkenes, sulfonamides and N‐(o‐bromothiophenol)succinimides
in a one‐pot procedure. As is shown in Table 4, various aromatic
alkenes, regardless of electron‐poor or ‐rich properties of
Scheme 2. Control experiments for intermolecular sulfenoamination reaction
R
S
O
N
BF •Et O
3
2
O
BF •Et O
3 2
2
N
O
O
Table 4. Substrate scope for the one‐pot synthesis of dihydrobenzothiazinesa
A
O
R2
N
O
R1
1
Succinimide
R
R
R2
RS
H
R2
S
S
R2
H NTs
R1
R1
2
NH Ts
NHTs
R1
2
B
C
4
Scheme 3. A Tentative mechanism for intermolecular sulfenoamintion
Based on these results and previous reports,2‐8, 13 a tentative
mechanism was proposed in Scheme 3. Initially, sulfenylating
agent
sulfenyl moiety to alkenes (
selective capture of intermediate
opposite side and subsequent deprotonation resulted in the
desired product in high diastereoselectivity.
Although the N‐sulfonyl groups are robust protecting groups
of amines, the present ‐sulfonylamino sulfides can be readily
desulfonated into the corresponding amines in high efficiency
Scheme 4). For example, the removal of N‐nosyl group of 4y
can be achieved in almost quantitative yield upon treatment
with K CO in the mixed solvent of DMSO/PhSH/CH CN; N‐
2
was activated by BF
3
∙Et
2
O and then transferred the
. Next,
on the
1
) forming thiiranium ion
B
14
B
with TsNH
2
4

a
Reaction conditions: (1) 1 (0.2 mmol), 2 (0.3 mmol), 3 (0.22 mmol), TfOH (0.04
o
mmol), in toluene (0.5 mL), at 60 C for 2 h; (2) Cu powder (0.22 mmol), in DMF (1
mL) at 120 C for 12 h under N
(
o
2
.
2
3
3
substitution on the aryl ring, could be transformed to the
corresponding dihydrobenzothiazines 11a in moderate to
‐
e
4
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ARTICLE
o
tosylated dihydrobenzothiazine 11a can be detosylated to 14 in 60‐90 C. Column chromatography was performed on silica gel
View Article Online
DOI: 10.1039/C7OB01225J
8
5% yield with the use of sodium naphthalide.
(200‐300 mesh) by using ester acetate and petroleum ether as
eluent.
General procedure for the synthesis of
. To a solution of alkene (0.3 mmol, 1.0 equiv), N‐
sulfanylsuccinimides (0.45 mmol, 1.5 equiv) and p‐
toluenesulfonamide (0.33 mmol, 1.1 equiv) in CH Cl (1.0 mL)
was added BF ∙Et O (0.06 mmol, 0.2 equiv) dropwise at room
‐sulfonamino sulfide
4
2
2
3
2
temperature. The reaction mixture was continuously stirred
until the starting material was consumed. The resulting mixture
was then quenched with H
2
O, extracted with ethyl acetate (3 ×
SO . After the organic
1
0 mL), and dried over anhydrous Na
2
4
Scheme 4. Desulfonation of 4w and 11a
solvent was removed under reduced pressure, the crude
product was purified by flash chromatography (Eluent:
PE/EtOAc = 90:10).
Conclusions
4
‐Methyl‐N‐(1‐phenyl‐2‐(p‐
1
5
In
conclusion,
an
acid‐catalyzed
intermolecular tolylthio)ethyl)benzenesulfonamide (4a). Yield: 120 mg (84%);
o
sulfenoamination reaction of alkenes with sulfonamides as time: 7 h; yellow solid; m.p. 100‐102 C; TLC, R
sources has been developed for the synthesis of various
f
= 0.35 (PE:EtOAc
1

‐
= 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.50 (d, 2H, J = 8.0 Hz), 7.22‐
sulfonylamino sulfides with high regio‐ and diastereoselectivity. 7.17 (m, 3H), 7.15‐7.10 (m, 4H), 7.09‐7.03 (m, 4H), 5.48‐5.30 (m,
Synthetically, the preparation of 4i can be scaled up in a 1H), 4.26 (q, 1H, J = 5.2 Hz), 3.14 (d, 2H, J = 7.2 Hz), 2.37 (s, 3H),
1
3
reduced catalyst loading (5 mol %) with no obvious loss of 2.34 (s, 3H); C NMR (CDCl
3
, 100 MHz): δ 143.2, 139.2, 137.1,
efficiency. Furthermore, by coupling with Cu‐mediated 136.8, 131.1, 130.2, 129.9, 129.3, 128.5, 127.9, 127.2, 126.8,
intramolecular C‐N bond formation, dihydrobenzothiazine 56.5, 41.9, 21.5, 21.1; HRMS (ESI) m/z calcd. for C22
27 2 2 2
H N O S
+
derivatives were also accessed through intermolecular [M+NH
4
] : 415.1508, found: 415.1516.
sulfenoamination of alkenes and intramolecular C‐N coupling in 4‐Methyl‐N‐(1‐(p‐tolyl)‐2‐(p‐
a one‐pot procedure. Both the N‐nosyl and ‐tosyl groups of tolylthio)ethyl)benzenesulfonamide (4b). Yield: 86.3 mg (70%);
o
products can be readily removed to release the corresponding time: 5 h; white solid; m.p. 89‐91 C; TLC, R
f
= 0.33 (PE:EtOAc =
1
amines. Mild reaction conditions, ready availability of starting 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.52 (d, 2H, J = 8.0 Hz), 7.18‐
materials, high reaction efficiency and selectivity, broad 7.09 (m, 4H), 7.06 (d, 2H, J = 8.0 Hz), 7.01 (d, 2H, J = 7.6 Hz), 6.96
substrate scope, as well as feasible desulfonation of products (d, 2H, J = 8.0 Hz), 5.45‐5.30 (m, 1H), 4.30‐4.12 (m, 1H), 3.24‐
make the present method valuable and practical for the 3.06 (m, 2H), 2.38 (s, 3H), 2.34 (s, 3H), 2.29 (s, 3H); 13C NMR
synthesis of various
derivatives.

3
‐amino sulfides and dihydrobenzothiazine (CDCl , 100 MHz): δ 143.1, 137.7, 137.0, 136.8, 136.2, 130.9,
130.4, 129.8, 129.3, 129.2, 127.2, 126.7, 56.3, 41.7, 21.4, 21.0;
+
HRMS (ESI) m/z calcd. for C23
found: 429.1661.
H
29
N
2
O
2
S
2
[M+NH
4
] : 429.1665,
Experimental
General information.
N‐(1‐(4‐Chlorophenyl)‐2‐(p‐tolylthio)ethyl)‐4‐
methylbenzenesulfonamide (4c). Yield: 114 mg (88%); time: 20
o
h; white solid; m.p. 138‐140 C; TLC, R
f
= 0.34 (PE:EtOAc = 8:2);
1H NMR spectra were recorded at 600 MHz or 400 MHz and 13
NMR spectra were measured at 150 MHz or 100 MHz using
NMR spectrometers with CDCl as the solvent. Chemical shifts
δ) were measured in ppm and referenced to the deuterated
C
1
3
H NMR (CDCl , 400 MHz): δ 7.49 (d, 2H, J = 8.0 Hz), 7. 18‐7.08
(
m, 6H), 7.05 (d, 2H, J = 8.0 Hz), 7.00 (d, 2H, J = 8.4 Hz), 5.40 (s,
3
1
3
1
2
4
H), 4.26 ‐4.16 (m, 1H), 3.14‐3.00 (m, 2H), 2.39 (s, 3H), 2.34 (s,
H); C NMR (CDCl , 100 MHz): δ 143.4, 137.7, 137.5, 136.6,
3
33.7, 131.3, 129.9, 129.8, 129.4, 128.6, 128.3, 127.2, 55.8, 41.9,
(
1
3
1
13
chloroform ( H: δ = 7.26 ppm, C: δ = 77.00 ppm). High‐
resolution mass spectrometry (HRMS) was performed on a TOF‐
Q spectrometer instrument with an ESI source. IR spectra were
recorded on a FT‐IR spectrometer in KBr pellets. Melting points
were measured with a RD‐II type melting point apparatus. X‐ray
structural analysis was obtained with an X‐ray single‐crystal
diffractometer. N‐Sulfanylsuccinimides are prepared following
previous reports and the known compounds are identified by
the comparison of their NMR spectra with reported data in
+
1.5, 21.1; HRMS (ESI) m/z calcd. for C22
H
26ClN
2
O
2
S
2
[M+NH
4
] :
49.1119, found: 449.1121.
N‐(1‐(2‐Chlorophenyl)‐2‐(p‐tolylthio)ethyl)‐4‐
methylbenzenesulfonamide (4d). Yield: 119.6 mg (92%); time:
o
5
1
h; white solid; m.p. 88‐90 C; TLC, R
f
= 0.35 (PE:EtOAc = 8:2);
3
H NMR (CDCl , 400 MHz): δ 7.57 (d, 2H, J = 8.4 Hz), 7. 39‐7.33
(
m, 1H), 7.23‐7.18 (m, 1H), 7.16‐7.09 (m, 4H), 7.08‐7.03 (m, 2H),
7
3
.00 (d, 2H, J = 8.0 Hz), 5.65 (d, 1H, J = 4.8 Hz), 4.76‐4.68 (m, 1H),
.28‐3.19 (m, 1H), 3.02‐2.93 (m, 1H), 2.36 (s, 3H), 2.31 (s, 3H);
C NMR (CDCl , 100 MHz): δ 143.2, 136.9, 136.8, 136.1, 132.0,
3
9
a
literatures. Unless otherwise noted, reagents obtained from
commercial sources were directly used without further
purification; all solvents were obtained from commercial
sources and were purified according to standard procedures.
Petroleum ether (PE), where used, has the boiling point range
1
3
1
2
4
30.8, 129.7, 129.6, 129.5, 129.3, 128.8, 127.2, 126.9, 53.4, 40.1,
+
1.4, 21.0; HRMS (ESI) m/z calcd. for C22
49.1119, found: 449.1113.
H
26ClN
2
O
2
S
2
[M+NH
4
] :
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 5
Please do not adjust margins

Org aP nl ei ca s &e dB oi on mo to al ed cj uu sl at rm Ca hr ge imn si stry
Page 6 of 11
ARTICLE
N‐(1‐(4‐Bromophenyl)‐2‐(p‐tolylthio)ethyl)‐4‐
Journal Name
4‐Methyl‐N‐(3‐oxo‐1,3‐diphenyl‐2‐(p‐
View Article Online
DOI: 10.1039/C7OB01225J
methylbenzenesulfonamide (4e). Yield: 88 mg (63%); time: 8 h; tolylthio)propyl)benzenesulfonamide (4j). Yield: 135.0 mg
o
1
o
white solid; m.p. 138‐140 C; TLC, R
NMR (CDCl
f
= 0.30 (PE:EtOAc = 8:2); H (90%); time: 18 h; white solid; m.p. 117‐119 C; TLC, R
f
= 0.30
1
3
, 400 MHz): δ 7.48 (d, 2H, J = 8.0 Hz), 7. 32‐7.26 (m, (PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.77 (d, 4H, J = 7.6
2
5
H), 7.16‐7.08 (m, 4H), 7.05 (d, 2H, J = 8.4 Hz), 6.97‐6.91 (m, 2H), Hz), 7.66 (t, 1H, J = 7.2 Hz), 7.48 (t, 2H, J = 7.6 Hz), 7.36 (d, 2H, J
.34 (d, 1H, J = 4.4 Hz), 4.23‐4.16 (m, 1H), 3.13‐2.99 (m, 2H), 2.40 = 8.0 Hz), 7.30‐7.22 (m, 9H), 7.02 (d, 1H, J = 7.6 Hz), 5.29‐5.21
1
3
13
(s, 3H), 2.34 (s, 3H); C NMR (CDCl
3
, 100 MHz): δ 143.5, 138.2, (m, 1H), 4.97 (d, 1H，J = 5.2 Hz), 2.54 (s, 3H), 2.52 (s, 3H); C
1
1
C
37.5, 136.6, 131.6, 131.4, 130.0, 129.7, 129.4, 128.6, 127.2, NMR (CDCl , 100 MHz): δ 197.0, 142.6, 139.2, 138.1, 137.8,
3
21.9, 55.9, 41.9, 21.5, 21.1; HRMS (ESI) m/z calcd. for 136.0, 134.3, 133.5, 129.9, 129.1, 129.0, 128.4, 128.3, 128.2,
+
22
H26BrN
2
O
2
S
2
[M+NH
4
] : 495.0593, found: 495.0591.
127.5, 127.04, 126.95, 59.9, 57.2, 21.3, 21.1; HRMS (ESI) m/z
+
N‐(1‐(3‐Bromophenyl)‐2‐(p‐tolylthio)ethyl)‐4‐
calcd. for C29
H
31
N
2
O
3
S
2
[M+NH
4
] : 519.1771, found: 519.1775.
methylbenzenesulfonamide (4f). Yield: 117.6 mg (84%); time: 6 N‐(3‐(4‐Methoxyphenyl)‐3‐oxo‐1‐phenyl‐2‐(p‐
o
1
h; white solid; m.p. 95‐97 C; TLC, R
f
= 0.34 (PE:EtOAc = 8:2); H tolylthio)propyl)‐4‐methylbenzenesulfonamide (4k). Yield: 91
= 0.28 (PE:EtOAc =
, 400 MHz): δ 7.59‐7.50 (m, 4H), 7.21‐7.15
.8 Hz), 4.28‐4.19 (m, 1H), 3.13‐3.00 (m, 2H), 2.38 (s, 3H), 2.33 (m, 2H), 7.11‐6.97 (m, 9H), 6.89 (d, 1H, J = 7.6 Hz), 6.73 (d, 2H, J
NMR (CDCl , 400 MHz): δ 7.50 (d, 2H, J = 8.4 Hz), 7.29‐7.25 (m, mg (88%); time: 18 h; colorless oil; TLC, R
H), 7.12 (d, 4H, J = 8.0 Hz), 7.09‐7.01 (m, 5H), 5.65 (d, 1H, J = 8:2); H NMR (CDCl
3
3
f
1
1
4
(
13
3
s, 3H); C NMR (CDCl , 100 MHz): δ 143.4, 141.4, 137.4, 136.6, = 8.8 Hz), 5.03‐4.95 (m, 1H), 4.70 (d, 1H, J = 4.4 Hz), 3.79 (s, 3H),
31.3, 130.8, 129.93, 129.89, 129.8, 129.3, 127.1, 125.6, 122.4, 2.33 (s, 3H), 2.31 (s, 3H); C NMR (CDCl , 100 MHz): δ 195.7,
3
6.0, 41.7, 21.5, 21.0; HRMS (ESI) m/z calcd. for C22
] : 493.0614, found: 493.0609.
‐Methyl‐N‐(1‐(naphthalen‐2‐yl)‐2‐(p‐
1
3
1
5
H26BrN
2
O
2
S
2
163.9, 142.6, 139.1, 138.4, 138.0, 134.3, 130.8, 130.0, 129.5,
+
[M+NH
4
129.0, 128.9, 128.2, 127.4, 127.1, 126.9, 113.7, 60.1, 56.8, 55.4,
+
4
21.4, 21.2; HRMS (ESI) m/z calcd. for C30
H
33
2
N O
4
S
2
[M+NH
4
] :
tolylthio)ethyl)benzenesulfonamide (4g). Yield: 89.3 mg (66%); 549.1876, found: 549.1888.
o
time: 4 h; white solid; m.p. 118‐120 C; TLC, R
f
= 0.31 (PE:EtOAc 4‐Methyl‐N‐(3‐(naphthalen‐2‐yl)‐3‐oxo‐1‐phenyl‐2‐(p‐
1
=
8:2); H NMR (CDCl
3
, 400 MHz): δ 7.79‐7.73 (m, 1H), 7.68‐7.62 tolylthio)propyl)benzenesulfonamide (4l). Yield: 83 mg (75%);
m, 2H), 7.52‐7.41 (m, 5H), 7.23‐7.11 (m, 3H), 7.05 (d, 2H, J = 7.6 time: 24 h; colorless oil; TLC, R
1
(
f
= 0.35 (PE:EtOAc = 8:2); H NMR
Hz), 6.98 (d, 2H, J = 8.0 Hz), 5.53 (d, 1H, J = 4.8 Hz), 4.49‐4.41(m, (CDCl
1
3
, 400 MHz): δ 7.83 (s, 1H), 7.78 (d, 1H, J = 8.0 Hz ), 7.73 (s,
H), 3.22 (d, 2H, J = 7.2 Hz), 2.33 (s, 3H), 2.25 (s, 3H); C NMR 2H), 7.63 (d, 1H, J = 8.0 Hz), 7.59‐7.51 (m, 3H), 7.49‐7.43 (m, 1H),
CDCl , 100 MHz): δ 143.2, 137.2, 136.8, 136.3, 132.95, 132.91, 7.15 (d, 2H, J = 8.0 Hz), 7.12‐6.98 (m, 9H), 6.87 (d, 1H, J = 8.8 Hz),
31.2, 130.2, 129.9, 129.2, 128.4, 127.8, 127.5, 127.2, 126.3, 5.17‐5.09 (m, 1H), 4.88 (d, 1H, J = 4.8 Hz), 2.29 (s, 3H), 2.26 (s,
1
3
(
3
1
1
1
3
26.12, 126.07, 124.3, 56.7, 41.8, 21.3, 21.0; HRMS (ESI) m/z 3H); C NMR (CDCl
3
, 100 MHz): δ 196.8, 142.7, 139.3, 138.2,
+
calcd. for C26
N‐(1,2‐Diphenyl‐2‐(p‐tolylthio)ethyl)‐4‐
H
29
N
2
O
2
S
2
[M+NH
4
] : 465.1665, found: 465.1663.
137.9, 135.6, 134.6, 133.4, 132.0, 130.5, 130.0, 129.6, 129.5,
129.0, 128.8, 128.3, 127.6, 127.5, 127.09, 127.06, 126.7, 123.8,
33 2 3 2
methylbenzenesulfonamide (4h). Yield: 104.0 mg (76%); time: 60.2, 57.5, 21.3, 21.1; HRMS (ESI) m/z calcd. for C33H N O S
o
+
6
h; white solid; m.p. 146‐148 C; TLC, R
f
= 0.30 (PE:EtOAc = 8:2); [M+NH
4
] : 569.1927, found: 569.1912.
1
H NMR (CDCl
3
, 400 MHz): δ 7.47 (d, 2H, J = 8.4 Hz), 7.24‐7.11 4‐Methyl‐N‐(3‐oxo‐3‐phenyl‐1‐(p‐tolyl)‐2‐(p‐
(
m, 4H), 7.10‐6.92 (m, 10H), 6.79 (d, 2H, J = 7.2 Hz), 5.48 (d, 1H, tolylthio)propyl)benzenesulfonamide (4m). Yield: 76 mg (75%);
o
J = 8.0 Hz), 4.80‐4.71 (m, 1H), 4.33 (d, 1H, J = 5.6 Hz), 2.32 (s, 3H), time: 28 h; white solid; m.p. 136‐138 C; TLC, R
2
f
= 0.36 (PE:EtOAc
1
3
1
3 3
.27 (s, 3H); C NMR (CDCl , 100 MHz): δ 142.9, 137.5, 137.4, = 8:2); H NMR (CDCl , 400 MHz): δ 7.65‐7.53 (m, 4H), 7.47 (t,
1
1
37.12, 137.09, 132.4, 130.3, 129.6, 129.1, 128.8, 128.3, 127.8, 1H, J = 7.2 Hz), 7.33‐7.26 (m, 2H), 7.16 (d, 2H, J = 8.0 Hz), 7.11‐
27.7, 127.57, 127.54, 127.1, 61.3, 61.0, 21.4, 21.0; HRMS (ESI) 7.01 (m, 4H), 6.98‐6.82 (m, 4H), 6.76‐6.64 (m, 1H), 5.00 (s, 1H),
+
13
31 2 2 2 4 3
m/z calcd. for C28H N O S [M+NH ] : 491.1821, found: 4.82‐4.69 (m, 1H), 2.33 (s, 6H), 2.18 (s, 3H); C NMR (CDCl , 100
4
4
91.1819.
‐Methyl‐N‐(1‐phenyl‐2‐(p‐
MHz): δ 197.0, 142.6, 139.1, 138.0, 137.2, 136.1, 135.1, 134.3,
133.4, 129.9, 129.2, 129.0, 128.9, 128.40, 128.38, 127.1, 126.9,
tolylthio)propyl)benzenesulfonamide (4i). Yield: 108.7 mg 59.8, 57.2, 21.3, 21.2, 20.9; HRMS (ESI) m/z calcd. for
+
(
1
93%); time: 8 h; colourless oil; TLC, R
f
= 0.37 (PE:EtOAc = 8:2);
C
30
H
33
N
2
O
3
S
2
[M+NH
4
] : 533.1927, found: 533.1933.
H NMR (CDCl
3
, 400 MHz, two isomers ratio: 2:1): δ 7.50 (d, N‐(1‐(4‐Chlorophenyl)‐3‐oxo‐3‐phenyl‐2‐(p‐tolylthio)propyl)‐
1
8
6
0
.36H, J = 8.0 Hz), 7.43 (d, 0.64H, J = 8.0 Hz), 7.23 (d, 0.74H, J = 4‐methylbenzenesulfonamide (4n). Yield: 93 mg (86%); time: 28
.4 Hz), 7.19‐7.00 (m, 10.3H), 5.86 (s, 0.34H), 5.46 (d, 0.68H, J = h; colorless oil; TLC, R = 0.34 (PE:EtOAc = 8:2); H NMR (CDCl ,
f 3
1
.0 Hz), 4.44‐4.37 (m, 0.69H), 4.13‐4.07 (m, 0.34H), 3.42‐3.32 (m, 400 MHz): δ 7.59 (d, 2H, J = 7.6 Hz), 7.55‐7.44 (m, 3H), 7.35‐7.27
.68H), 3.24‐3.14 m, 0.35H), 2.34 (d, 6H, J = 6.4 Hz), 1.15 (d, 2H, (m, 2H), 7.20‐6.90 (m, 10H), 6.82‐6.65 (m, 1H), 5.50‐4.93 (m, 1H),
1
3
13
3 3
J = 7.2 Hz), 1.02 (d, 1H, J = 6.8 Hz); C NMR (CDCl , 100 MHz): δ 4.71 (d, 1H, J = 4.8 Hz), 2.34 (s, 3H), 2.33 (s, 3H); C NMR (CDCl ,
1
1
6
43.0, 137.7, 137.5, 137.0, 134.3, 132.7, 130.0, 129.9, 129.8, 100 MHz): δ 196.4, 143.0, 139.3, 137.6, 136.6, 135.8, 134.4,
29.2, 129.1, 128.1, 128.0, 127.7, 127.6, 127.5, 127.4, 127.2, 133.6, 133.4, 130.0, 129.1, 128.7, 128.6, 128.5, 128.4, 128.3,
1.6, 60.2, 51.1, 49.5, 21.4, 21.14, 21.12, 18.4, 16.7; HRMS (ESI) 127.0, 59.3, 56.8, 21.3, 21.1; HRMS (ESI) m/z calcd. for
+
+
m/z calcd. for C23
4
H
29
N
2
O
2
S
2
[M+NH
4
] : 429.1665, found:
C
29
H
30ClN
2
O
3
S
2
[M+NH
3‐(4‐methylphenylsulfonamido)‐3‐phenyl‐2‐(p‐
tolylthio)propanoate (4o) Yield: 128.4 mg (94%); time: 17 h;
4
] : 533.1381, found: 533.1387.
29.1666.
Methyl
.
6
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 11
Org aP nl ei ca s &e dB oi on mo to al ed cj uu sl at rm Ca hr ge imn si stry
Journal Name
ARTICLE
o
1
white solid; m.p. 136‐138 C; TLC, R
NMR (CDCl
f
= 0.39 (PE:EtOAc = 8:2); H (26.7), 21.5, 21.0, 19.8, 19.6, 15.5. HRMS (ESI) m/z calcd. for
View Article Online
DOI: 10.1039/C7OB01225J
+
3
, 400 MHz): δ 7.57 (d, 2H, J = 8.4 Hz), 7.22 (d, 2H, J =
24 3 2
C H30NO S [M+H] : 444.1662, found: 444.1651.
8
2
3
.0 Hz ), 7.18‐7.11 (m, 3H), 7.08 (t, 4H, J = 7.6 Hz), 7.04‐7.00 (m, 3‐(p‐Tolylthio)‐1‐tosylpyrrolidine (8). Yield: 96.8 mg (93%); time:
1
H), 6.29‐6.20 (m, 1H), 4.89‐4.83 (m, 1H), 3.84 (d, 1H, J = 5.6 Hz), 6 h; colorless oil; TLC, R
.51 (s, 3H), 2.33 (d, 6H, J = 4.0 Hz); 13C NMR (CDCl
f 3
= 0.46 (PE:EtOAc = 8:2); H NMR (CDCl ,
3
, 100 MHz): 400 MHz): δ 7.69 (d, 2H, J = 8.4 Hz), 7.32 (d, 2H, J = 8.0 Hz), 7.21‐
δ 171.0, 142.9, 138.8, 137.71, 137.68, 137.7, 133.6, 129.9, 129.2, 7.15 (m, 2H), 7.09 (d, 2H, J = 8.0 Hz), 3.68‐3.60 (m, 1H), 3.58‐
1
2
4
4
29.1, 129.2, 128.4, 127.8, 127.1, 126.6, 59.0, 57.4, 52.4, 21.4, 3.49 (m, 1H), 3.36 (t, 2H, J = 7.2 Hz), 3.14‐3.07 (m, 1H), 2.44 (s,
+
13
1.1; HRMS (ESI) m/z calcd. for C24
73.1563, found: 473.1563.
H
29
2
N O
4
S
2
[M+NH
4
] : 3H), 2.33 (s, 3H), 2.20‐2.09 (m, 1H), 1.81‐1.70 (m, 1H); C NMR
(CDCl , 100 MHz): δ 143.6, 137.9, 133.7, 132.6, 130.0, 129.9,
3
‐Methyl‐N‐(1‐(p‐tolylthio)octan‐2‐yl)benzenesulfonamide
129.7, 127.6, 53.7, 46.9, 45.2, 31.8, 21.6, 21.1; HRMS (ESI) m/z
+
(
4p). Yield: 92.0 mg (77%); time: 18 h; colorless oil; TLC, R
f
= 0.48 calcd. for C18
H
22NO
2
S
2
[M+H] : 348.1086, found: 348.1098.
1
(
PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.65 (d, 2H, J = 8.4 2‐((p‐Tolylthio)methyl)‐1‐tosylpyrrolidine (9). Yield: 104.0 mg
o
Hz), 7.21 (d, 2H, J = 8.0 Hz), 7.16 (d, 2H, J = 8.0 Hz), 7.07 (d, 2H, (96%); time: 5 h; white solid; m.p. 78‐80 C; TLC, R
J = 8.0 Hz), 4.93 (d, 1H, J = 8.0 Hz), 3.37‐3.25 (m, 1H), 3.12‐3.02 (PE:EtOAc = 8:2); H NMR (CDCl
f
= 0.46
1
3
, 400 MHz): δ 7.54 (d, 2H, J = 8.4
(
(
m, 1H), 2.79‐2.69 (m, 1H), 2.39 (s, 3H), 2.33 (s, 3H), 1.68‐1.56 Hz), 7.39‐7.33 (m, 2H, ), 7.23 (d, 2H, J = 8.0 Hz), 7.16 (d, 2H, J =
m, 1H), 1.45‐1.32 (m, 1H), 1.23‐0.96 (m, 8H), 0.83 (t, 3H, J = 7.2 8.0 Hz), 3.68‐3.55 (m, 2H), 3.51‐3.44 (m, 1H), 3.14‐3.04 (m, 1H),
1
3
3
Hz); C NMR (CDCl , 100 MHz): δ 143.2, 137.5, 136.6, 131.5, 2.79‐2.68 (m, 1H), 2.40 (s, 3H), 2.36 (s, 3H), 1.94‐1.73 (m, 2H),
1
2
1
3
3
30.5, 129.7, 129.5, 127.0, 52.9, 39.9, 33.5, 31.5, 28.7, 25.1, 1.68‐1.61 (m, 1H); C NMR (CDCl , 100 MHz): δ 143.4, 136.2,
2.4, 21.4, 21.0, 14.0; HRMS (ESI) m/z calcd. for C22
M+H] : 406.1869, found: 406.1877.
H
32NO
2
S
2
133.9, 131.6, 129.8, 129.7, 129.6, 127.5, 59.0, 49.7, 39.0, 30.2,
+
+
[
27.8, 21.5, 21.1; HRMS (ESI) m/z calcd. for C19
H
24NO
2
S
2
[M+H] :
4
‐Methyl‐N‐(2‐(p‐tolylthio)cyclohexyl)benzenesulfonamide
362.1243, found: 362.1247.
o
(
4q). Yield: 82.2 mg (73%); time: 14 h; white solid; m.p. 90‐92 C; 4‐Methyl‐N‐(1‐phenyl‐2‐
1
TLC, R
f
= 0.40 (PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.76 (phenylthio)ethyl)benzenesulfonamide (4t). Yield: 105.3mg
o
(
d, 2H, J = 8.4 Hz), 7.29 (d, 2H, J = 8.0 Hz), 7.15 (d, 2H, J = 8.0 Hz), (91%); time: 6 h; white solid; m.p. 104‐106 C; TLC, R
f
= 0.36
1
7
2
2
.05 (d, 2H, J = 8.0 Hz), 5.36 (d, 1H, J = 4.0 Hz), 3.00‐2.88 (m, 1H), (PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.51 (d, 2H, J = 8.4
.85‐2.74 (m, 1H), 2.44 (s, 3H), 2.33 (s, 3H), 2.32‐2.24 (m, 1H), Hz), 7.26‐7.18 (m, 8H), 7.12 (d, 2H, J = 8.0 Hz), 7.10‐7.05 (m, 2H),
1
3
.04‐1.94 (m, 1H), 1.65‐1.52 (m, 2H), 1.34‐1.16 (m, 4H); C NMR 5.33 (s, 1H), 4.35‐4.23 (m, 1H), 3.27‐3.13 (m, 2H), 2.37 (s, 3H);
13
(CDCl
3
, 100 MHz): δ 143.3, 138.0, 137.2, 133.9, 129.7, 129.6,
3
C NMR (CDCl , 100 MHz): δ 143.3, 139.1, 136.7, 134.1, 130.3,
1
28.5, 127.3, 55.3, 51.8, 32.5, 31.8, 24.8, 23.4, 21.5, 21.1; HRMS 129.4, 129.1, 128.6, 128.0, 127.2, 126.83, 126.77, 56.5, 41.1,
+
+
(
ESI) m/z calcd. for C20
76.1398.
‐(2‐( ‐Tolylthio)‐1‐(
H26NO
2
S
2
[M+H] : 376.1399, found: 21.5; HRMS (ESI) m/z calcd. for C21
H
25
2
N O
2
S
2
[M+NH
4
] :
3
3
1
=
2
6
4
2
1
401.1352, found: 401.1350.
p
p
‐tosylamino)ethyl
)
‐1,3,5(10
)
‐estratrien‐
N‐(2‐((4‐Methoxyphenyl)thio)‐1‐phenylethyl)‐4‐
7‐one (4r). Yield: 120 mg (70%); time:6 h; colorless oil; TLC, R
f
methylbenzenesulfonamide (4u). Yield: 112.4 mg (90%); time:
1
o
0.36 (PE:EtOAc = 7:3); H NMR (CDCl
3
, 400 MHz): δ 7.51 (dd, 16 h; yellow solid; m.p. 113‐115 C; TLC, R
f
= 0.36 (PE:EtOAc =
1
H, J = 8.0, 4.4 Hz), 7.15‐7.09 (m, 5H), 7.05 (d, 2H, J = 8.0 Hz), 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.50 (d, 2H, J = 8.4 Hz), 7.22‐
.85 (t, 1H, J = 6.0 Hz), 6.74 (s, 1H), 5.32 (dd, 1H, J = 6.8, 4.8 Hz), 7.15 (m, 5H), 7.12 (d, 2H, J = 8.0Hz), 7.08‐7.02 (m, 2H), 6.82‐6.76
.24‐4.16 (m, 1H), 3.14 (dd, 2H, J = 6.8, 3.6 Hz), 2.78‐2.66 (m, (m, 2H), 5.44 (s, 1H), 4.26‐4.17 (m, 1H), 3.81 (s, 3H), 3.07 (d, 2H,
1
3
H), 2.51 (dd, 1H, J = 9.4, 8.8 Hz), 2.38 (s, 3H), 2.33 (s, 3H), 2.26‐ J = 6.8 Hz), 2.38 (s, 3H); C NMR (CDCl
3
, 100 MHz): δ 159.4,
1
3
.95 (m, 6H), 1.68‐1.30 (m, 5H), 0.91 (d, 3H, J = 2.8 Hz); C NMR 143.1, 139.2, 136.8, 134.0, 129.3, 128.4, 127.8, 127.2, 126.8,
(
CDCl
3
, 100 MHz): δ 220.7, 143.0, 139.5, 137.0, 136.9, 136.5, 124.1, 114.7, 56.5, 55.3, 43.1, 21.4; HRMS (ESI) m/z calcd. for
+
1
1
2
C
36.4, 131.0, 130.9, 130.4, 129.8, 129.2, 127.4, 127.3, 125.4,
24.3, 56.2, 50.4, 47.9, 44.3, 41.6, 38.0, 35.8, 31.5, 29.2, 26.4, N‐(2‐((4‐Chlorophenyl)thio)‐1‐phenylethyl)‐4‐
5.6, 21.6, 21.5, 21.0, 13.8. HRMS (ESI) m/z calcd. for methylbenzenesulfonamide (4v). Yield: 84.0 mg (68%); time: 20
C
22
H
27
N
2
O
3
S
2
[M+NH
4
] : 431.1458, found: 431.1466.
+
o
34
H39NO
3
S
p
2
Na [M+Na] : 596.2264, found: 596.2261.
‐Tolylthio)‐2‐( ‐tosylamino)propan‐2‐yl)‐2‐
h; white solid; m.p. 128‐130 C; TLC, R
f
= 0.33 (PE:EtOAc = 8:2);
1
(
5R)‐5‐(1‐(
p
3
H NMR (CDCl , 400 MHz): δ 7.51 (d, 2H, J = 8.4 Hz), 7.24‐7.18
methylcyclohex‐2‐en‐1‐one (4s). Yield: 113 mg (85%); time: 3 h; (m, 5H), 7.17‐7.10 (m, 4H), 7.08‐7.02 (m, 2H), 5.25‐5.14 (m, 1H),
1
13
colorless oil; TLC, R
f
= 0.40 (PE:EtOAc = 7:3) ; H NMR (CDCl
3
, 400 4.30‐4.20 (m, 1H), 3.28‐3.13 (m, 2H), 2.38 (s, 3H); C NMR
, 100 MHz): δ 143.5, 138.9, 136.6, 133.0, 132.6, 131.7,
MHz, two isomers): δ 7.15 (d, 1H, J = 8.4 Hz), 7.78 (d, 1H, J = 8.0 (CDCl
3
Hz), 7.24‐7.14 (m, 4H), 7.11‐7.05 (m, 2H), 6.66 (dd, 1H, J = 28.4, 129.4, 129.2, 128.7, 128.2, 127.2, 126.7, 56.4, 41.3, 21.5; HRMS
+
6
(
.0 Hz), 5.52 (d, 1H, J = 30.0 Hz), 3.14 (d, 0.5H, J = 13.2 Hz), 3.08 (ESI) m/z calcd. for C21
s, 1H), 2.93 (d, 0.5H, J = 13.2 Hz), 2.60‐2.40 (m, 2H), 2.39 (d, 3H, 435.0957.
J = 2.4 Hz), 2.35‐2.29 (m, 4H), 2.20‐2.05 (m, 2H), 1.74 (s, 3H), N‐(2‐((2‐Bromophenyl)thio)‐1‐phenylethyl)‐4‐
H
24ClN
2
O
2
S
2
[M+NH
4
] : 435.0962, found:
13
1
.19 (d, 3H, J = 4.0 Hz). C NMR (CDCl
3
, 100 MHz): δ 198.8 methylbenzenesulfonamide (4w). Yield: 100.0 mg (73%); time:
o
(
198.4), 144.6, 143.9, 143.3 (143.2), 139.7 (139.6), 137.1 (137.0), 18 h; white solid; m.p. 128‐130 C; TLC, R
f
= 0.33 (PE:EtOAc =
, 400 MHz): δ 7.54 (t, 3H, J = 5.2 Hz), 7.25‐
1
1
35.4 (135.3), 131.9 (131.8), 131.0, 130.9, 129.9, 129.6, 127.0 8:2); H NMR (CDCl
3
(
126.9), 61.1 (61.0), 44.9 (44.8), 42.8, 42.5, 38.9 (38.8), 26.9 7.18 (m, 5H), 7.16‐7.09 (m, 4H), 7.08‐7.02 (m, 1H), 5.33‐5.24 (m,
1
H), 4.42‐4.32 (m, 1H), 3.25 (d, 2H, J = 6.8 Hz), 2.35 (s, 3H); 13
C
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 7
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Org aP nl ei ca s &e dB oi on mo to al ed cj uu sl at rm Ca hr ge imn si stry
Page 8 of 11
ARTICLE
Journal Name
3
, 100 MHz): δ 143.3, 139.0, 136.6, 135.5, 133.2, mmol, 0.2 equiv) dropwise at room temperature. The reaction
NMR (CDCl
View Article Online
DOI: 10.1039/C7OB01225J
o
1
5
29.7, 129.4, 128.7, 128.1, 127.8, 127.6, 127.1, 126.7, 124.8, mixture was stirred at 60 C for 2 h and a solution of copper
6.2, 40.1, 21.5; HRMS (ESI) m/z calcd. for C21
H24BrN
2
O
2
S
2
powder (0.22 mmol, 1.1 equiv) in DMF (1.0 mL) was then added.
+
o
[M+NH
4
] : 479.0457, found: 479.0449.
After stirring for another 12 h at 120 C under argon, the
4
‐Methyl‐N‐(2‐(naphthalen‐2‐ylthio)‐1‐
resulting mixture was cooled to room temperature, washed
phenylethyl)benzenesulfonamide (4x). Yield: 87.0 mg (67%); with water, and extracted with ethyl acetate (3 × 10 mL), and
o
time: 5 h; white solid; m.p. 118‐120 C; TLC, R
f
= 0.40 (PE:EtOAc dried over anhydrous Na
2
SO
4
. The organic solvent was removed
1
=
8:2); H NMR (CDCl
3
, 400 MHz): δ 7.84‐7.78 (m, 1H), 7.76‐7.69 under reduced pressure, and the crude product was purified by
(
m, 2H), 7.68‐7.65 (m, 1H), 7.55‐7.44 (m, 4H), 7.29 (dd, 1H, J = flash chromatography (Eluent: PE/EtOAc = 20:1).
8
=
.0, 2.0 Hz), 7.25‐7.19 (m, 3H), 7.14‐7.07 (m, 2H), 6.97 (d, 2H, J 3‐Phenyl‐4‐tosyl‐3,4‐dihydro‐2H‐benzo[b][1,4]thiazine
(
11a).
o
8.0 Hz), 5.41 (d, 1H, J = 4.8 Hz), 4.39‐4.28 (m, 1H), 3.40‐3.24 Yield: 54.6 mg (72%); time: 14 h; white solid; m.p. 119‐121 C;
1
3
1
(
3 f 3
m, 2H), 2.24 (s, 3H); C NMR (CDCl , 100 MHz): δ 143.2, 139.1, TLC, R = 0.36 (PE:EtOAc = 20:1); H NMR (CDCl , 400 MHz): δ
1
1
36.4, 133.6, 132.0, 131.5, 129.3, 128.64, 128.60, 128.3, 128.1, 7.81 (d, 1H, J = 8.0 Hz), 7.46‐7.37 (m, 4H), 7.34‐7.27 (m, 2H),
27.7, 127.5, 127.2, 127.1, 126.8, 126.7, 126.1, 56.5, 40.7, 21.3; 7.26‐7.15 (m, 4H), 7.12‐7.05 (m, 2H), 5.73 (t, 1H, J = 6.8 Hz),
+
13
HRMS (ESI) m/z calcd. for C25
found: 451.1503.
H
27
N
2
O
2
S
2
[M+NH
4
] : 451.1508, 3.26‐3.18 (m, 1H), 3.03‐2.95 (m, 1H), 2.40 (s, 3H); C NMR
(CDCl , 100 MHz): δ 143.7, 139.8, 136.1, 134.5, 132.2, 130.0,
3
N‐(2‐(Ethylthio)‐1‐phenylethyl)‐4‐methylbenzenesulfonamide
129.4, 128.6, 128.2, 127.6, 127.4, 126.4, 126.3, 126.1, 60.8, 34.5,
+
(
4y). Yield: 67 mg (67%); time: 18 h; colorless oil; TLC, R
f
= 0.44 21.6; HRMS (ESI) m/z calcd. for C21
H
23
2
N O
2
S
2
[M+NH
4
] :
1
(
PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.59 (d, 2H, J = 8.4 399.1195, found: 399.1198.
Hz), 7.22‐7.16 (m, 4H), 7.16‐7.10 (m, 3H), 5.57 (d, 1H, J = 4.8 Hz), 3‐(p‐Tolyl)‐4‐tosyl‐3,4‐dihydro‐2H‐benzo[b][1,4]thiazine (11b)
.
4
2
1
2
3
.40‐4.30 (m, 1H), 2.91‐2.71 (m, 2H), 2.37 (s, 3H), 2.32‐2.18 (m, Yield: 44.2 mg (56%); time: 16 h; white solid; m.p. 138‐140
1
3
o
1
H), 1.12 (t, 3H, J = 7.2 Hz); C NMR (CDCl
3
, 100 MHz): δ 143.2,
C;TLC, R
f
= 0.34 (PE:EtOAc = 20:1); H NMR (CDCl
3
, 400 MHz): δ
39.6,136.9, 129.3, 128.4, 127.7, 127.2, 126.7, 56.4, 38.8, 25.7, 7.79 (d, 1H, J = 8.0 Hz), 7.43 (d, 2H, J = 8.4 Hz ), 7.28 (d, 2H, J =
+
1.4, 14.3; HRMS (ESI) m/z calcd. for C17
H
25
2
N O
2
S
2
[M+NH
4
] : 8.0 Hz), 7.21‐7.15 (m, 3H), 7.12‐7.06 (m, 4H), 5.70 (t, 1H, J = 6.4
Hz), 3.24‐3.16 (m, 1H), 3.04‐2.95 (m, 1H), 2.40 (s, 3H), 2.29 (s,
53.1352, found: 353.1368.
1
3
N‐(1‐Phenyl‐2‐(p‐tolylthio)ethyl)benzenesulfonamide
Yield: 91.0 mg (80%); time: 10 h; yellow solid; m.p. 86‐88 C; TLC, 134.4, 132.0, 129.9, 129.4, 129.3, 128.1, 127.4, 126.4, 126.3,
R
(4z)
.
3
3H); C NMR (CDCl , 100 MHz): δ 143.7, 137.3, 136.7, 136.2,
o
1
f
= 0.36 (PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.62 (d, 126.0, 60.2, 34.1, 21.6, 21.0; HRMS (ESI) m/z calcd. for
+
2
7
4
1
1
H, J = 8.4 Hz), 7.46 (t, 1H, J = 7.2Hz), 7.32 (t, 2H, J = 7.6 Hz ),
C
22
H22NO
2
S
2
[M+H] : 396.1086, found: 396.1084.
.21‐7.11 (m, 5H), 7.10‐7.02 (m, 4H), 5.62‐5.46 (m, 1H), 4.35‐ 3‐(2‐Chlorophenyl)‐4‐tosyl‐3,4‐dihydro‐2H‐
1
3
.26 (m, 1H), 3.15 (d, 2H, J = 6.8 Hz), 2.34 (s, 3H); C NMR (CDCl
3
,
benzo[b][1,4]thiazine (11c). Yield: 59.6 mg (74%); time: 14 h;
o
00 MHz): δ 139.8, 139.0, 137.2, 132.3, 131.2, 130.2, 129.9, white solid; m.p. 169‐171 C; TLC, R
28.7, 128.5, 127.9, 127.1, 126.8, 55.6, 41.9, 21.0; HRMS (ESI)
] : 401.1352, found: J = 7.6 Hz), 7.44‐7.31 (m, 4H), 7.29‐7.22 (m, 2H), 7.22‐7.14 (m,
4H), 5.97‐5.90 (m, 1H), 3.40‐3.31 (m, 1H), 2.64‐2.54 (m, 1H),
‐Nitro‐N‐(1‐Phenyl‐2‐(p‐tolylthio)ethyl)benzenesulfonamide
f
= 0.35 (PE:EtOAc = 20:1);
H NMR (CDCl , 400 MHz): δ 7.95 (d, 1H, J = 8.4 Hz), 7.53 (d, 1H,
3
1
+
m/z calcd. for C21
4
4
H
25
N
2
O
2
S
2
[M+NH
4
01.1362.
1
3
3
2.39 (s, 3H); C NMR (CDCl , 100 MHz): δ 143.7, 139.5, 136.5,
(
1
4aa). Yield: 91.0 mg (71%); time: 12 h; yellow solid; m.p. 148‐ 135.11, 135.08, 131.3, 130.2, 129.6, 129.4, 129.3, 128.9, 127.6,
o
1
50 C; TLC, R
f
= 0.31 (PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): 127.5, 127.2, 126.6, 62.8, 37.1, 21.6; HRMS (ESI) m/z calcd. for
+
δ 8.06 (d, 2H, J = 8.8 Hz), 7.68 (d, 2H, J = 8.8 Hz), 7.22‐7.13 (m,
C
21
H22ClN
2
O
2
S
2
[M+NH
4
] : 433.0806, found: 433.0799.
5
3
H), 7.12‐7.02 (m, 4H), 5.68‐5.59 (m, 1H), 4.39‐4.30 (m, 1H), 3‐(3‐Bromophenyl)‐4‐tosyl‐3,4‐dihydro‐2H‐
.26‐3.16 (m, 1H), 3.09‐2.98 (m, 1H), 2.34 (s, 3H); 13C NMR benzo[b][1,4]thiazine (11d). Yield: 62.5 mg (71%); time: 12 h;
o
(CDCl
3
, 100 MHz): δ 149.6, 145.6, 138.5, 137.7, 130.9, 130.1, white solid; m.p. 140‐142 C; TLC, R
f
= 0.34 (PE:EtOAc = 20:1);
1
1
29.5, 128.7, 128.3, 126.9, 123.7, 55.5, 41.5, 21.0; HRMS (ESI)
3
H NMR (CDCl , 400 MHz): δ 7.85‐7.81 (m, 1H), 7.54‐7.50 (m,
] : 446.1203, found: 1H), 7.43‐7.31 (m, 4H), 7.26‐7.15 (m, 4H), 7.14‐7.07 (m, 2H),
5.69‐5.62 (m, 1H), 3.23‐3.13 (m, 1H), 2.96‐2.86 (m, 1H), 2.40 (s,
+
m/z calcd. for C21
46.1197.
H
24
N
3
O
4
S
2
[M+NH
4
4
1
3
N‐(1‐Phenyl‐2‐(p‐tolylthio)ethyl)methanesulfonamide
Yield: 79.6 mg (83%); time: 8 h; yellow solid; m.p. 75‐77 C; TLC, 132.3, 130.8, 130.2, 130.0, 129.44, 129.43, 128.4, 127.4, 126.6,
R
7
3
(4bb). 3H); C NMR (CDCl , 100 MHz): δ 143.9, 142.3, 135.7 134.3,
o
1
f
= 0.36 (PE:EtOAc = 8:2); H NMR (CDCl
3
, 400 MHz): δ 7.39‐ 126.4, 125.0, 122.7, 60.7, 34.7, 21.6; HRMS (ESI) m/z calcd. for
+
.27 (m, 7H), 7.13 (d, 2H, J = 8.0 Hz), 5.45 (s, 1H), 4.55‐4.46 (m,
C
21
H19BrNO
2
S
2
[M+H] : 460.0035, found: 460.0031.
1
3
1
H), 3.30‐3.22 (m, 1H), 3.18‐3.08 (m, 1H), 2.62 (s, 3H), 2.34 (s, 6‐Methyl‐3‐phenyl‐4‐tosyl‐3,4‐dihydro‐2H‐
H); 1 C NMR (CDCl
3
, 100 MHz): δ 139.8, 137.5, 131.3, 130.0
，
benzo[b][1,4]thiazine (11e). Yield: 79 mg (91%); time: 14 h;
3
o
28.9, 128.4, 126.9, 56.6, 42.1, 41.8, 21.0; HRMS (ESI) m/z calcd. white solid; m.p. 122‐124 C; TLC, R
f
= 0.32 (PE:EtOAc = 20:1);
+
1
for C16
H
23
N
2
O
2
S
2
[M+NH
4
] : 339.1195, found: 339.1196.
3
H NMR (CDCl , 400 MHz): δ 7.65 (s, 1H), 7.46‐7.37 (m, 4H), 7.31
Preparation
benzo[
equiv) and 1‐((2‐bromophenyl)thio)pyrrolidine‐2,5‐dione (0.30 1H), 2.98‐2.86 (m, 1H), 2.40 (s, 3H), 2.37 (s, 3H); C NMR (CDCl
mmol, 1.5 equiv) in toluene (0.5 mL) was added TfOH (0.04 100 MHz): δ 143.6, 140.2, 136.3, 136.0, 134.5, 130.5, 129.3,
of
3‐phenyl‐4‐tosyl‐3,4‐dihydro‐2
H‐
(t, 2H, J = 7.6 Hz), 7.26‐7.21 (m, 1H), 7.18 (d, 2H, J = 8.4 Hz), 7.02‐
b
][1,4]thiazine. To a solution of olefin (0.20 mmol, 1.0 6.97 (m, 1H), 6.95‐6.90 (m, 1H), 5.72‐5.65 (m, 1H), 3.24‐3.14 (m,
1
3
3
,
8
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
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Page 9 of 11
Org aP nl ei ca s &e dB oi on mo to al ed cj uu sl at rm Ca hr ge imn si stry
Journal Name
ARTICLE
1
2
3
4
29.1, 128.6, 128.0, 127.6, 127.42, 127.38, 126.3, 61.6, 35.3,
1.6, 21.2; HRMS (ESI) m/z calcd. for C22H22NO S [M+H] :
2 2
96.1086, found: 396.1087.
‐(Methylsulfonyl)‐3‐phenyl‐3,4‐dihydro‐2H‐
Acknowledgements
This work was supported by the Natural Science Foundation of
Shanxi Province (No. 2015021037), Scientific and Technological
Innovation Programs of Higher Education Institutions in Shanxi
View Article Online
DOI: 10.1039/C7OB01225J
+
benzo[b][1,4]thiazine (11f). Yield: 42.0 mg (69%); time: 22 h;
(
(
STIP) (No. 2015133) and the China Scholarship Council (CSC)
No. 201608140185). We thank Dr. Wei Cao (Shanxi University)
o
1
white solid; m.p. 99‐101 C; TLC, R
NMR (CDCl , 400 MHz): δ 7.71 (dd, 1H, J = 8.0, 1.2 Hz), 7.37‐7.27
m, 5H), 7.26‐7.21 (m, 2H), 7.20‐7.15 (m, 1H), 5.76‐5.69 (m, 1H),
f
= 0.34 (PE:EtOAc = 20:1); H
3
for determination of all the X‐ray crystal structures.
(
3
.55‐3.46 (m, 1H), 3.13‐3.04 (m, 1H), 2.89 (s, 3H); 13C NMR
, 100 MHz): δ 140.3, 135.4, 133.0, 129.8, 129.2, 128.7,
(CDCl
3
Notes and references
1
27.8, 127.2, 126.8, 126.1, 63.0, 38.3, 37.4; HRMS (ESI) m/z
+
1
(a) N. A. McGrath, M. Brichacek, and J. T. Njardarson, J. Chem.
Educ., 2010, 87, 1348; (b) V. Cecchetti, V. Calderone, O.
Tabarrini, S. Sabatini, E. Filipponi, L. Testai, R. Spogli, E.
Martinotti, and A. Fravolini, J. Med. Chem., 2003, 46, 3670; (c)
Y. Wei, L.‐Q. Lu, T.‐R. Li, B. Feng, Q. Wang, W.‐J. Xiao, and H.
Alper, Angew. Chem. Int. Ed., 2016, 55, 2200.
calcd. for C15
1
H
16NO
2
S
2
[M+H] : 306.0617, found: 306.0607.
0‐Tosyl‐2,3,4,4a,10,10a‐hexahydro‐1H‐phenothiazine (11g).
o
Yield: 44.7mg (65%); time: 20 h; white solid, mp 116‐118 C; TLC,
R
1
f
= 0.34 (PE:EtOAc = 20:1); H NMR (CDCl
3
, 400 MHz): δ 7.74 (d,
1H, J = 8.0 Hz), 7.25‐7.18 (m, 3H), 7.13‐7.05 (m, 4H), 3.92‐3.80
2
(a) S. E. Denmark, and H. M. Chi, J. Am. Chem. Soc., 2014, 136
,
(
m, 1H), 2.62‐2.53 (m, 1H), 2.49‐2.40 (m, 1H), 2.35 (s, 3H), 2.10‐
8
915; (b) S. E. Denmark, E. Hartmann, D. J. P. Kornfilt, H. Wang,
1
1
1
2
3
.99 (m, 1H), 1.88‐1.72 (m, 2H), 1.60‐1.35 (m, 3H), 1.30‐1.15 (m,
Nat. Chem., 2014,
6
, 1056; (c) L. Li, Z. Li, D. Huang, H. Wang, Y.
1
3
3
H); C NMR (CDCl , 100 MHz): δ 143.3, 136.0, 135.5, 134.6,
Shi, RSC Adv., 2013, 3, 4523.
30.3, 129.4, 128.9, 127.4, 126.6, 126.2, 70.2, 51.8, 36.3, 31.7,
3
4
P. Mizar, R. Niebuhr, M. Hutchings, and U. Farooq, T. Wirth,
+
Chem. Eur. J., 2016, 22, 1614.
5.6, 24.8, 21.5; HRMS (ESI) m/z calcd. for C19
H
22NO
2
S
2
[M+H] :
For
other
examples
about
the
intermolecular
60.1086, found: 360.1079.
difunctionalization of olefins, see: (a) F. Wang, D. Wang, X.
Wan, L. Wu, P. Chen, and G. Liu, J. Am. Chem. Soc., 2016, 138
5547; (b) S. M. Banik, J. W. Medley, and E. N. Jacobsen, J. Am.
Preparation of 1‐phenyl‐2‐(
stirred mixture of 4y (64.6 mg, 0.15 mmol), K
mmol) and DMSO (0.1 mL) in CH
p
‐tolylthio)ethanamine (13).1c To a
CO (84 mg, 0.6
CN (3.0 mL) was added PhSH
,
2
3
1
3
Chem. Soc., 2016, 138, 5000; (c) J. L. Kennemur, G. D. Kortman,
and K. L. Hull, J. Am. Chem. Soc., 2016, 138, 11914.
o
(
0.1 mL). Upon stirring at 50 C for 6 h, the resulting mixture was
5
6
(a) M. Tiecco, M. Tingoli, L. Testaferri, and R. Balducci, J. Org.
Chem., 1992, 57, 4025; (b) V. Lucchini, G. Modena, and L.
Pasquato, J. Chem. Soc., Chem. Commun., 1994, 1565.
(a) Y. Zheng, Y. He, G. Rong, X. Zhang, Y. Weng, K. Dong, X. Xu,
and J. Mao, Org. Lett., 2015, 17, 5444; (b) H. Cui, X. Liu, W.
Wei, D. Yang, C. He, T. Zhang, and H. Wang, J. Org. Chem.,
concentrated to remove CH
NH
over anhydrous Na
under reduced pressure, the crude product was purified by flash
3
CN, washed with saturated aq.
Cl (3 × 10 mL), and dried
4
. After the organic solvent was removed
4
Cl and brine, extracted with CH
SO
2
2
2
chromatography (Eluent: PE/EtOAc = 7:3) to give 13. Yield: 36.2
2
016, 81, 2252; (c) D. Wang, Z. Yan, Q. Xie, R. Zhang, S. Lin,
mg (99%); time: 6 h; colorless oil; TLC, R
f
= 0.28 (PE:EtOAc = 7:3);
and Y. Wang, Org. Biomol. Chem., 2017, 15, 1998.
1
H NMR (CDCl
3
, 400 MHz): δ 7.32‐7.25 (m, 6H), 7.24 (m, 1H),
7
8
(a) D. Li, T. Mao, J. Huang, and Zhu, Q. Chem. Commun., 2017,
7
.11 (d, 2H, J = 8.0 Hz), 4.04 (dd, 1H, J = 9.6, 3.6 Hz), 3.28‐3.21
53, 3450; (b) G. Zheng, J. Zhao, Z. Li, Q. Zhang, J. Sun, H. Sun,
1
3
(
(
1
m, 1H, ), 3.01‐2.90 (m, 1H), 2.31 (s, 3H), 1.88 (brs, 2H); C NMR
CDCl , 100 MHz): δ 144.2, 136.5, 131.8, 130.5, 129.8, 128.5,
27.4, 126.4, 54.5, 44.5, 21.0.
Preparation of 3‐phenyl‐3,4‐dihydro‐2H‐benzo[
and Q. Zhang, Chem. Eur. J., 2016, 22, 3513.
For selected examples, see: (a) P. Saravanan, and P.
Anbarasan, Org. Lett., 2014, 16, 848; (b) T. Hostier, V. Ferey,
G. Ricci, D. G. Pardo, and J. Cossy, Org. Lett., 2015, 17, 3898;
3
b
][1,4]thiazine
To a solution of sodium (32.2 mg, 1.4 mmol) in dry THF
2.0 mL) was added naphthalene (167.0 mg, 1.30 mmol) in dry
(
c) T. Hostier, V. Ferey, G. Ricci, D. G. Pardo, and J. Cossy, Chem.
16
(
(
14).
Commun., 2015, 51, 13898.
9
(a) W.‐C. Gao, T. Liu, B. Zhang, X. Li, W.‐L. Wei, Q. Liu, J. Tian,
and H.‐H. Chang, J. Org. Chem. 2016, 81, 11297; (b) W.‐C. Gao,
F. Hu, J. Tian, X. Li, W.‐L. Wei, and H.‐H. Chang, Chem.
Commun. 2016, 52, 13097; (c) W.‐C. Gao, F. Hu, Y.‐M. Huo, H.‐
H. Chang, X. Li, and W.‐L. Wei, Org. Lett. 2015, 17, 3914; (d)
W.‐C. Gao, J.‐J. Zhao, F. Hu, H.‐H. Chang, X. Li, and W.‐L. Wei,
THF (2.0 mL) and stirred at room temperature for 4 h. 11a (76.0
mg, 0.20 mmol) in dry THF (2.0 mL) was subjected to the above
mentioned solution of sodium naphthalide at ‐78 C. After
complete disappearance of starting materials (monitored by
TLC), the reaction was quenched with saturated aq. NH
extracted with ethyl acetate (3 × 10 mL). After thhe combined
organic layer was dried over anhydrous Na SO and
concentrated under reduced pressure, the crude product was
purified by flash chromatography (Eluent: PE/EtOAc = 50:1).
o
4
Cl and
RSC Adv., 2015,
X. Li, Q. Liu, and W.‐L. Wei, RSC Adv., 2014,
0 (a) H. Tian, J. Yu, H. Yang, C. Zhu, and H. Fu, Adv. Synth. Catal.,
5, 25222; (e) W.‐C. Gao, J.‐J. Zhao, H.‐H. Chang,
4
, 49329.
1
1
2
4
2
016, 358, 1794; (b) J. Yu, M. Jiang, Z. Song, T. He, H. Yang,
and H. Fu, Adv. Synth. Catal., 2016, 358, 2806.
1 (a) R.‐H. Fan, and X.‐L. Hou, J. Org. Chem., 2003, 68, 726; (b) J.
Yield: 38.6 mg (85%); time: 2 h; colorless oil; TLC, R
f
= 0.40
Wu, X. Sun, and W. Sun, Org. Biomol. Chem., 2006, 4, 4231; (c)
1
Q. Yang, Z. Yin, M. Yang, and Y. Peng, Chin. J. Chem., 2011, 29
,
(
PE:EtOAc = 50:1); H NMR (CDCl
3
, 400 MHz): δ 7.44‐7.31 (m,
7
9; (d) M. K. Ghorai, M. Sayyad, Y. Nanaji, S. Jana, Chem. Asian
5
(
4
H), 7.08 (dd, 1H, J = 7.6, 1.2 Hz), 6.98‐6.91 (m, 1H), 6.72‐6.63
m, 1H), 6.54 (d, 1H, J = 8.0 Hz), 4.68 (dd, 1H, J = 8.8, 2.8 Hz),
.16 (s, 1H), 3.24‐3.12 (m, 1H), 3.06‐2.98 (m, 1H); 13C NMR
J., 2015, 10, 1480; (e) F. Zeng, and H. Alper, Org. Lett., 2010,
1
2
2
, 5567; (f) D. J. C. Prasad, and G. Sekar, Org. Biomol. Chem.,
009, , 5091.
7
(CDCl
3
, 100 MHz): δ 142.8, 142.2, 128.9, 128.2, 127.4, 126.7, 12 (a) A. Macchiarulo, G. Costantino, D. Fringuelli, A. Vecchiarelli,
F. Chiaffella, and R. Fringuelli, Bioorg. Med. Chem., 2002, 10
,
1
25.6, 118.3, 115.4, 115.3, 56.1, 33.1.
3
415; (b) F. Corelli, F. Manetti, A. Tafi, G. Campiani, V. Nacci,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 9
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Org aP nl ei ca s &e dB oi on mo to al ed cj uu sl at rm Ca hr ge imn si stry
Page 10 of 11
ARTICLE
and M. Botta, J. Med. Chem., 1997, 40, 125; (c) V. Calderone,
Journal Name
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Res., 1979, 12, 282.
DOI: 10.1039/C7OB01225J
1
1
4 Regiochemistry was determined by electronic factors
(
Markovnikov selectivity), as amination mainly occurs at the
benzylic carbon of aryl alkenes and branched carbon of
aliphatic alkenes.
5 A. Toshimitsu, H. Abe, C. Hirosawa, and K. Tamao, J. Chem. Soc.
Perkin Trans. 1, 1994, 3465.
6 D.‐A. Gruzdev, E.‐N. Chulakov, L.‐S. Sadretdinova, M. Kodess,
1
1
G.‐L. Levit, V.‐P. Krasnov, Tetrahedron: Asymmetry, 2015, 26
,
1
86.
1
0 | J. Name., 2012, 00, 1‐3
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Page 11 of 11
Organic & Biomolecular Chemistry
View Article Online
DOI: 10.1039/C7OB01225J
An acid-catalyzed intermolecular sulfenoamination of alkenes is developed with sulfonylamides
as N-source, enabling the synthesis of β-sulfonylamino sulfides and dihydrobenzothiazines.