Metal-free I2O5-mediated direct construction of sulfonamides from thiols and amines

Article abstract of DOI:10.1039/c7ob00668c

A simple and convenient method has been developed for the construction of sulfonamides via I₂O₅-mediated sulfonylation of amines with arylthiols. The present protocol provides an attractive approach to sulfonamides in moderate to good yields from readily accessible and easy to handle starting materials under mild and metal-free conditions.

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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Metal-free I2O5 -mediated direct construction of sulfonamides from thiols and
amines†
Minghui Zhu, Wei Wei*, Daoshan Yang, Huanhuan Cui, Leilei Wang, Guoqing Meng, Hua Wang*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
nucleophilic reaction of amino compounds on sulfonyl chlorides
promoted by a base.5 However, this method suffer from the
difficulty in handling and storing of sulfonyl chlorides and poor
40 functional group tolerance. To obviate these drawbacks, some
alternative methods have been developed, including the metal-
A simple and convenient method has been developed for the
construction of sulfonamides via I2O5-mediated sulfonylation
of amines with arylthiols. The present protocol provides an
attractive approach to sulfonamides in moderate to good
10 yields from readily accessible and easy to handle starting
materials under mild and metal-free conditions.
catalyzed
coupling
reaction
of
N-unsubstituted/N-
monosubstituted sulfonamides with organic halides,6 arylboronic
acids,7 alcohols,8 aryl nonaflates,9 or hydrocarbons,10 the
45 aminosulfonylation reactions of aryl halides, boronic acids and
diazoniumsalts,11 the conversion of N-tosylhydrazones to
sulfonamides through reaction with sulfur dioxide and an
amine,12 the oxidative coupling of amines and sodium sulfinates13
As an important class of sulfonyl-containing compounds,
sulfonamides are frequently found in a large number of nature
products, biologically active compounds, and pharmaceuticals.1
15 In particular, sulfonamide derivatives exhibit a wide range of
biological activities such as anticancer, antibacterial,
anticonvulsant, anti-inflammatory, and antiviral and HIV protease
inhibitory.2 Some representative pharmaceutically important drug
candidates including Sildenafil, Amprenavir, E7070, and
20 Glibencamide are shown in Figure 1.3 In addition, sulfonamides
can also be used as protecting groups in synthetic chemistry due
to the easy removal of sulfonamide group under mild conditions.4
thiosulfonates,14
or
sulfonyl
hydrazides.15
50 Nevertheless, most of the methods mentioned above for the
preparation of sulfonamides usually need toxic metal catalysts,
extra steps to prepare the starting materials, multistep reactions,
or relatively hash reaction conditions. Therefore, the development
of simple, mild, convenient, and efficient method to access
55 sulfonamides from simple and readily available starting materials
is still highly desirable.
Recently, the direct using of thiols to construct sulfonamides
have attracted increasingly interests of chemists because of its
easy availability, low cost, and high atom economy.16-18 Bahrami
60 and co-workers reported the direct oxidative conversion of thiols
into sulfonamides in the presence of H2O2-ZrCl4 or H2O2-POCl3
system.16 Taniguchi described CuI-bpy catalyzed oxidative
coupling of arylthiols with primary amines leading to
sulfonamides under an oxygen atmosphere.17 In 2014, Pan and
65 co-workers reported CuCl-mediated protocol for the synthesis of
sulfonamides from arylthiols and formamides assisted by a
stoichiometric amount of Cu(OAc)2 and cinnamic acid.18
Nevertheless, these well developed reactions still require the use
of transition metal catalysts or potentially dangerous peroxide
70 oxidants, which may limit their wide applications on a large scale
in the synthetic and pharmaceutical chemistry.
O
e
M
N
N
O
O
N
O
O
N
O
O
S
S
N
H
O
N
H
N
OH
t
OE
N
NH2
e
M
ena
Sild
m
renav r
fil
A
p
i
H
N
O
NHCy
O
S
O
O
O
Cl
S
e
M
N
O
H
NH
H
O
S
N
NH2
e
OM
O
enc am
e
id
Glib
l
E7070
Figure 1 Pharmacologically active molecules with sulfonamide structure
25 motif.
During the past several decades, considerable efforts have
been dedicated in the construction of sulfonamides and many
useful synthetic methods have been successfully developed. The
traditional method for preparing sulfonamides is by the
R2
R3
O
S
R2
R3
e
u v
q
1 i
I2O5
(
)
1
(
)
N
+
SH
HN
CH3CN 60oC 12h
,
,
R1
R1
O
a
30
Institute of Medicine and Material Applied Technologies, Key
Laboratory of Pharmaceutical Intermediates and Analysis of Natural
Medicine, School of Chemistry and Chemical Engineering, Qufu Normal
As part of our continuous interest in the metal-free synthetic
transformations,13d,19 herein, we wish to report a simple and
75 convenient metal-free I2O5-mediated protocol for the construction
of sulfonamides via direct oxidative coupling of with various
University,
Qufu
273165,
Shandong, China.
E-mail:
weiweiqfnu@163.com; huawang_qfnu@126.com
35 † Electronic Supplementary Information (ESI) available: Experimental
details. See DOI: 10.1039/b000000x/
This journal is © The Royal Society of Chemistry [year]
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DOI: 10.1039/C7OB00P66a8gCe 2 of 5
arylthiols and amines (eqn (1)).
Table 1 Optimization of the reaction conditionsa
tolerated in this chemistry with the formation of the desired
product 3l in 75% yield. Notably, heteroarylthiol such as
40 pyridine-4-thiol was also suitable substrate leading to the desired
product 3m in 60% yield. Nevertheless, when alkylthiols such as
butane-1-thiol and 2-phenylethanethiol were employed in the
present reaction system, none of the desired products were
detected. Subsequently, the participation of amines in this
45 protocol was examined. In addition to morpholine, other cyclic
secondary amines such as piperidine and pyrrolidine were also
compatible with this reaction to furnish the corresponding
products (3n and 3o) in 64% and 56% yields, respectively.
Furthermore, benzylamine and its derivatives, which have
50 electron-rich or electron poor groups on the aryl rings, could
readily participate in the reactions to deliver the sulfonamides
3p−3u in moderate to good yields. Other primary aliphatic
amines such as butan-1-amine and 2-methoxyethanamine were
also used in this transformation to give the corresponding
55 products (3v and 3w) in moderate yields. In the these cases, using
DBU as the base was necessary. As expected, aromatic amine
such as p-toluidine was also appropriate for the reaction, but
leading to the desired product 3x in the relatively low yield.
O
S
I2O5
+
H3C
SH
H3C
N
O
HN
O
S
l
t
To
C
,
o ven
O
a
a
2
a
3
1
Entry
1
Solvent
DCE
T(oC)
80
Yield (%)b
26
2
3
4
5
THF
CH3CN
DMSO
DMF
80
80
80
80
8
53
trace
trace
6
7
8
9
DME
80
80
80
80
trace
Toluene
0
0
0
1,4-dioxane
H2O
10
11
12
13
14
CH3CN
CH3CN
80
80
60
25
60
71c
82d
82d
10d
79d,e
CH3CN
CH3CN
CH3CN
Table 2 Results for I2O5 mediated direct construction of sulfonamides
60 from arylthiols and aminesab,
15
60
0f
CH3CN
R2
R3
O
S
R2
e
u v
q
1 i
a
I2O5
(
)
Reaction conditions: 1) 1a (0.2 mmol), 2a (0.2 mmol), I2O5 (1 equiv),
+
SH
HN
N
5 solvent (2 mL), 25-80°C, air, 12 h. b Isolated yields based on 1a. c 2a (0.3
mmol). d 2a (0.4 mmol). e I2O5 (1.5 equiv). f without of I2O5.
CH3CN 60oC 12h
,
,
R1
R1
R3
O
1
2
3
O
S
O
O
H
3C
N
O
H
3CO
S
N
O
O
S
N
O
Initially, the 4-methylbenzenethiol 1a (0.2 mmol) and
morpholine 2a (0.2 mmol) were used as model substrates to
10 determine the optimized reaction conditions in the presence I2O5
(1 equiv). To our delight, the desired product 3a was obtained in
26% yield when the reaction was conducted in DCE at 80oC for
12h (Table 1, entry 1). Further optimization of solvents suggested
that CH3CN was the best reaction medium, affording the desired
15 product in 53% yield (Table 1, entry 3). In contrast, only a trace
amount of product was detected when the reaction was performed
in DMSO, DMF or DME (Table 1, entries 4-6). The reaction did
not occur in toluene, 1,4-dioxane, or H2O (Table 1, entries 7-9).
Notably, the reaction efficiency was significantly improved when
20 the quantity of morpholine 2a was increased to 2 equivalents
(Table 1, entries 10 and 11). The optimized reaction temperature
is 60oC (Table 1, entry 12). The low yield was observed when the
reaction was performed at room temperature (Table 1, entry 13).
Moreover, the increase of the loading of I2O5 did not improve
25 the reactivity (Table 1, entry 14). Additionally, no product was
detected when the reaction was conducted in the absence of I2O5,
which indicated that I2O5 was essential to this reaction (Table 1,
entry 15).
With the standard reaction conditions in hand, we moved on
30 to study the scope and generality of this reaction using various
thiols and amines. In general, aryl thiols bearing electron-rich or -
poor groups on the aryl rings were suitable for this reaction,
affording the desired products in good yields (3a−3k). It should
be noted that this transformation was not significantly affected by
35 the steric effect. The steric encumbered ortho- or meta-substituted
aryl thiols were also effectively used in this reaction to give
products 3d−3g in good yields. 2-Naphthalenethiol was well
O
O
O
a
c
85
(
3
82
%
)
3
%
)
(
3b 81%
(
)
H
3C
O
S
O
S
O
S
N
O
H
3CO
H
N
N
O
O
O
O
CH3
3CO
e
3d 88%
3
85%
3f 81%
( )
(
)
(
)
O
S
O
S
O
S
H
3C
N
O
N
O
Cl
F
N
O
O
O
O
C
H
3
3g 67%
3h 81%
(
3i 75%
(
(
)
)
)
O
O
O
S
N
O
S
S
N
O
r
B
N
O
O
O
O
Cl
3
86%
)
3k 62%
(
3l 75%
(
j (
)
)
O
O
O
S
H
3C
S
N
H
3C
S
N
N
N
O
O
O
O
o
3
n
3
5
6%
)
m
64%
(
(
3
60%
)
)
(
O
S
O
S
CH3
F
O
S
H
3C
NH
H
3C
NH
H
3C
NH
O
O
O
3p 63% c
3q 60% c
1
%
)
c
r
3 6
(
(
)
(
)
r
B
O
S
O
r
B
O
Cl
H
3C
NH
H
3C
S
NH
c
H
3C
S
NH
O
O
O
60% c
s
3
6
7
%
)
(
3t 53% c
u
x
(
)
3
(
)
O
O
O
O
S
H
H
3C
S
N
CH3
H
3C
S
NH
H
3C
NH
O
O
O
56% c
42% c
v
3
w
3
57% c
3
(
)
(
)
(
)
a
Reaction conditions: 1) 1 (0.2 mmol), 2 (0.4 mmol), I2O5 (1 equiv),
CH3CN (2 mL), 60°C, air, 12h; Isolated yields based on 1. DBU (0.2
65 mmol).
b
c
Furthermore, the synthetic applicability of this transformation
was investigated on a gram scale by using the reaction of 1a and
2a. As shown in eqn (2), the model reaction could produce 1.95g
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Organic & Biomolecular Chemistry
in Scheme 1. Firstly, the dimerization of thiol 1 generated
30 disulfide 4, which was oxidized by I2O5 to give
benzenesulfonothioate 5 with the concomitant formation of
of 3a in 81% yield without significant loss of reaction efficiency,
indicating that this method could serve as a practical protocol to
synthesize sulfonamides.
molecular
iodine.
Subsequently,
the
interaction
of
O
e
u v
q
i
I2O5
1
,
(
)
benzenesulfonothioate 5 with iodine produced sulfonyl iodide 6.
Finally, the nucleophilic substitution of sulfonyl iodide 6 by
35 amine 2 would lead the formation of the desired sulfonamide 3.
In conclusion, a new metal-free I2O5-mediated strategy for
facile synthesis of sulfonamides from various arylthiols and
amines has been developed. The present method provides a
simple and efficient approach to a variety of sulfonamides in
40 moderate to good yields from readily-available starting materials
under mild reaction conditions. Moreover, it can avoid the risk of
metal contamination and the use of potentially dangerous
peroxide oxidants. Further applications of this method are under
investigation in our laboratory
2
( )
+
H3C
SH
H3C
S
N
,
O
HN
O
CH3CN 60oC 12h
,
O
.
a
2
mmo
a
mmo
l
)
20
l
)
1
10
a
(
(
3
1 95g 81%
(
)
5
To obtain some insights into this reaction, several control
experiments were carried out. Initially, when the reaction of 4-
methylbenzenethiol 2a with I2O5 was conducted for 15 min, 1,2-
dip-tolyldisulfane 4a and p-tolyl 4-methylbenzenesulfonothioate
5a were isolated in 40% and 29% yields, respectively (eqn (3)).
10 Furthermore, p-tolyl 4-methylbenzenesulfonothioate 5a was
obtained in 62% yield when the reaction of 4-methylbenzenethiol
2a with I2O5 was conducted for 3h (eqn (4)). Moreover, the
oxidation of 1,2-dip-tolyldisulfane 4a by I2O5 produced p-tolyl 4-
methylbenzenesulfonothioate 5a in 65% yield, indicating that p-
15 tolyl 4-methylbenzenesulfonothioate 5a might be formed from
the oxidation of 1,2-dip-tolyldisulfane (eqn (5)). In addition, the
sulfonyl iodide 4a was detected when 4-methylbenzenethiol 2a
was subjected to the reaction in the presence of I2O5. When the
reaction of sulfonyl iodide 4a with morpholine 2a was performed
20 in the absence of CH3CN at 60oC, the desired sulfonamide 3a was
obtained in 86% yield (eqn (6)). The above results suggested that
sulfonyl iodide might be the key intermediate in the present
reaction system.
45
This work was supported by the National Natural Science
Foundation of China (No. 21302109, 21302110, 21375075, and
21675099), the Natural Science Foundation of Shandong
Province (ZR2015JL004 and ZR2016JL012), and the Taishan
Scholar Foundation of Shandong Province.
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60
65
70
S
S
e
u v
i
)
I2O5
,
1
q
(
a
4
40
%
(
)
SH
3
(
)
+
CH3CN 60oC 15
,
m n
i
O
S
.
a
2
mmo
l
)
0 4
(
S
O
a
5
29
%
(
)
O
S
e
u v
q
1 i
I2O5
(
)
4
5
S
SH
(
)
2
(a) M. Mariusz, K. Zbigniew, W. Waldemar, C. Mariangela, T.
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CH3CN 60oC 3h
,
,
O
62
.
a
2
mmo
l
)
a
0 4
5
%
)
(
(
O
S
e
u v
i
)
I2O5
1
(
,
q
S
S
(
)
S
CH3CN 60oC 3h
,
O
.
a
2
mmo
a
5
65
(
0 2
l
%
)
(
)
O
S
O
S
CH3CN
6
N
O
(
)
+
HN
O
I
60oC 12h
,
O
O
a
a
2
a
86%
(
6
3
)
75 3
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25
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I2O5
80
O
I2
O
[
]
r
r
A
r
r
r
A
A
S
S
A
S
H
A
S
S
O
5
I2
1
4
R2
R3
85
HN
R2
R3
4
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O
O
2
r
r
A
S
N
A
I
S
O
O
6
3
90
Scheme 1. Tentative reaction pathway
5
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Page 5 of 5
Organic & Biomolecular Chemistry
View Article Online
DOI: 10.1039/C7OB00668C
A simple and efficient metal-free I2O5-mediated one-pot procedure for the
construction of sulfonamides from thiols and amines has been developed.