Fe-based metal-organic frameworks for the synthesis of N-arylsulfonamides via the reactions of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes in water

Article abstract of DOI:10.1016/j.tetlet.2018.10.032

A newly developed chemoselective reaction of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes has been disclosed. The chemistry, in which non-toxic water and recyclable iron-based metal-organic frameworks are employed as the solvent and catalyst, respectively, provides an efficient approach for the generation of N-arylsulfonamides, which are widely present in biologically active compounds and drugs, rendering this methodology attractive to both synthetic and medicinal chemistry.

Full text of DOI:10.1016/j.tetlet.2018.10.032

Accepted Manuscript
Fe-Based metal-organic frameworks for the synthesis of N-arylsulfonamides
via the reactions of sodium arylsulfinates or arylsulfonyl chlorides with nitro-
arenes in water
Xinxin Li, Fei Chen, Guo-Ping Lu
PII:
S0040-4039(18)31250-4
https://doi.org/10.1016/j.tetlet.2018.10.032
TETL 50342
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
5 August 2018
12 October 2018
17 October 2018
Please cite this article as: Li, X., Chen, F., Lu, G-P., Fe-Based metal-organic frameworks for the synthesis of N-
arylsulfonamides via the reactions of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes in water,
Tetrahedron Letters (2018), doi: https://doi.org/10.1016/j.tetlet.2018.10.032
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Fe-Based metal-organic frameworks for the synthesis of N-
arylsulfonamides via the reactions of sodium arylsulfinates or
arylsulfonyl chlorides with nitroarenes in water
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Xinxin Li, Fei Chen, Guo-Ping Lu
Tetrahedron Letters
journal homepage: www.elsevier.com
Fe-Based metal-organic frameworks for the synthesis of N-arylsulfonamides via the
reactions of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes in water
Xinxin Lia, Fei Chenb and Guo-Ping Lua,*
a School of Chemical Engineering, Nanjing University of Science & Technology, Xiaolingwei 200, Nanjing 210094, P. R. China.
b Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection, Jiangwangmiao 8, Nanjing 210042, Jiangsu, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A newly developed chemoselective reaction of sodium arylsulfinates or arylsulfonyl chlorides
with nitroarenes has been disclosed. The chemistry, in which non-toxic water and recyclable
iron-based metal-organic frameworks are employed as the solvent and catalyst, respectively,
provides an efficient approach for the generation of N-arylsulfonamides, which are widely
present in biologically active compounds and drugs, rendering this methodology attractive to
both synthetic and medicinal chemistry.
Available online
Keywords:
2018 Elsevier Ltd. All rights reserved.
Fe-based metal-organic frameworks
N-Arylsulfonamides
Nitroarenes
Sodium arylsulfinates
Arylsulfonyl chlorides
Water
1. Introduction
N-Arylsulfonamides are a significant class of building blocks that are widely present in biologically active compounds and drugs.1
As such, a large number of approaches have been developed for the synthesis of these compounds.2 A classical route towards N-
arylsulfonamides is the amination of arylsulfonyl chlorides (arylsulfonate esters or arylsulfinates) with aromatic amines.3 However,
aromatic amines are genotoxic and unstable, which may result in undesired impurities during the preparation of active pharmaceutical
ingredients.4 Moreover, protection and deprotection sequences may be required when the amines contain reactive groups such as
hydroxyl, amino and aldehyde groups. To avoid the use of amines, several transition-metal-catalyzed transformations for the
construction of N-arylsulfonamides via C-N bond formation have been reported.5 Nevertheless, these strategies suffer from limitations,
including harsh conditions, the use of transition metal catalysts, and the requirement of additional bases, ligands or prefabricated
starting materials.
To overcome these issues, stable and inexpensive nitroarenes have emerged as a highly attractive nitrogen source for the synthesis of
N-arylsulfonamides. In 2015, Luo and co-workers reported an efficient and convenient iron-catalyzed system for the direct construction
of sulfonamides from nitroarenes and sodium arylsulfinates.6 In 2016, a palladium-catalyzed method for the construction of these

compounds from nitroarenes and arylsulfonyl hydrazides was developed by Deng and co-workers.7 In 2018, Xiang and co-workers
introduced a Fe-promoted protocol for the synthesis of these compounds from nitroarenes and sulfonyl chlorides.8 Guided by the
principles of green chemistry9 and in line with our interests in exploring the reactions of sodium arylsulfinates in water for the
formation of organic sulphur compounds,10 we envisaged the reaction of nitroarenes with sodium arylsulfinates for the synthesis of N-
arylsulfonamides in water using a recyclable and inexpensive metal catalyst.
Metal-organic frameworks (MOFs) have appeared as promising heterogeneous catalysts for various transformations, such as
oxidations,11 reductions12 and condensations,13 mostly on the basis of their Lewis acid sites offered by unsaturated metal centers,14 and
optical activities offered by the inorganic cluster nodes, the organic linkers or the guests in the pores of MOFs.15 Therefore, we reasoned
that Fe-based MOFs could be employed as recyclable Lewis acid catalysts for the coupling of nitroarenes with sodium arylsulfinates in
the place of iron salts. Along this line, we report an efficient and highly chemoselective protocol for the synthesis of N-arylsulfonamides
via the MIL-101(Fe) catalyzed coupling of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes in water.
2. Results and Discussion
Initially, the model reaction of nitrobenzene 1a and sodium p-tolylsulfinate was selected to optimize the reaction conditions. After
screening different iron sources, Fe-MOFs were shown to result in better yields than iron salts (Table 1, entries 1-5), presumably owing
to their stable structure and strong Lewis acidity.12b,14 MIL-101(Fe) was selected for further studies because its starting materials were
cheaper and the procedure for
_______
*Corresponding author. Tel.: +86 25 84315514; fax: +86 25 84315030. E-mail address: glu@njust.edu.cn
Table 1. Reaction conditions optimization.a
O
S
NO2
SO2Na
H
N
cat. Fe
+
Ph
NaHSO3
O
1a
2a
3a
Yield 3a (%)b
70
74
97
aReagents and conditions: 1a (0.5 mmol), 2a (1.0 mmol), NaHSO3 (1.0 mmol), catalyst (10
mg, 8 mol% of Fe), solvent (2 mL), 60 °C, 12 h. bGC yield. c40 mg of catalyst was used. d20
mg of catalyst was used. e4 mg of catalyst was used. fNo reaction.
Entry Catalyst
Solvent
1
2
FeCl2
FeCl3
H2O
H2O
3
4
5
6
MIL-100(Fe) H2O
MIL-53(Fe) H2O
MIL-101(Fe) H2O
H2O
98
O
S
SO2Na
H
MIL-101(Fe)
NaHSO3
96,c 91,d 95, 63e
Ar NO2
+
Ar
N
-
34
1
2a
3
O
H2O, 60 o
C
7
8
9
10
11
12
13
14
15
16
MIL-101(Fe) DMSO
MIL-101(Fe) CH2Cl2
MIL-101(Fe) THF
MIL-101(Fe) EtOAc
MIL-101(Fe) CH3CN
93
nrf
O
S
O
trace
H
H
nrf
N
S
N
Cl
nrf
O
O
3a,
3b
, 79%
91%
MIL-101(Fe) n-Hexane nrf
H2N
H2N
MIL-101(Fe) DMAc
MIL-101(Fe) NMP
MIL-101(Fe) DME
MIL-101(Fe) EtOH
nrf
24
trace
trace
O
S
O
H
H
N
S
N
O
O
, 78%
Cl
CF3
a
3c
3e
3d
, 82%
F
O
H
O
N
H
S
N
S
N
O
O
3f
, 90%
, 80%
O
S
O
H
N
H
N
OMe
S
CHO
O
3g
O
3h
, 67%
, 92%
COOMe
O
S
O
H
H
N
S
N
O
O
a
3i
, 86%
3j
, 58%
O
S
O
H
H
N
S
N
Ph
O
O
3k
, nr
3l
, nr
Scheme 1. Reactions of nitroarenes with sodium p-tolylsulfinate. Reagents and conditions: 1 (0.5 mmol), 2a (1 mmol), NaHSO3 (1 mmol),
MIL-101(Fe) (10 mg, 8 mol% of Fe), H2O (2 mL), 60 °C, 20 h; isolated yield. aDMSO/H2O (v/v =1:1, 2 mL).

O
S
MIL-101(Fe)
H
+ Ar SO2Na
NO2
O
Ar
N
NaHSO3, H2O
60 oC, 20 h
O
1a
2
3
O
H
H
N
N
S
Cl
S
O
O
, 91%
3m
3n
, 93%
O
S
O
H
H
N
OMe
N
S
NHCOCH3
O
O
3o
, 86%
3p
, 83%
O
S
O
S
F
F
F
H
O
H
SO2NHPh
, nr
Ph
N
Ph
N
O
, nr
O
, nr
3q
3r
3t
Scheme 2. Reactions of nitrobenzene with sodium arylsulfinates. Reagents and conditions: 1a (0.5 mmol), 2 (1 mmol), NaHSO3 (1 mmol),
MIL-101(Fe) (10 mg, 8 mol% of Fe), H2O (2 mL), 60 °C, 20 h; isolated yield.
the synthesis of MIL-101(Fe) was simpler than the other two Fe-MOFs.14b The optimized amount of MIL-Fe(101) was 10 mg (Entry 5).
A low yield of 3a (34%) was observed in the absence of MIL-Fe(101) (Entry 6). Several organic solvents were also examined (Entries
7-16); only DMSO was comparable to water and provided an excellent yield of 3a.
With the optimized conditions in hands, a series of nitroarenes were chosen to establish the scope and generality of the protocol
(Scheme 1). Both electron-rich and electron-deficient nitroarenes reacted with 1a to give the desired products (3a-j). In general,
electron-rich nitroarenes were less reactive than electron-deficient ones, and only moderate yields of 3c, 3g and 3j were obtained. It
should be noted that the desired products (3c-e, 3h) were also formed when the nitroarenes with reactive groups were used. A mixture
of DMSO and water as the solvent was required for the formation of both 3d and 3j owing to the poor solubility of the nitroarenes.
Nitromethane and (E)-(2-nitrovinyl)-benzene failed to give the desired products (3k, 3l). The electronic effects of the substituents on the
sodium arylsulfinates have no obvious influence on the reaction; sodium arylsulfinates with electron-withdrawing and electron-donating
groups reacted with nitrobenzene to give 3m-p in good to excellent yields (Scheme 2). However, sodium alkylsulfinates including
sodium methyl-, trifluoromethyl- and camphorsulfinates failed to give the desired products 3q-t.
To further demonstrate the potential of this methodology, two nitroarenes 4 and 6 (prepared via an SNAr reaction),16 were coupled
with the corresponding sodium arylsulfinates to form N-arylsulfonamides 5 and 7, which are potentially useful in the treatment of
tumors17 and peptic ulcers,18 respectively (Scheme 3). Compound 9 (an aquaporin-4 function promoter and pharmaceutical composition
for neurological disorders),19 was also synthesized from 8 (Scheme 3). It should be noted that a mixture of DMSO and water was
necessary due to the poor solubility of nitroarenes 4, 6 and 8 in water. Compared with the previous approaches,16-19 no reduction of the
nitroarene was required, and better chemoselectivity and yields were obtained.
O
S
F
NHPh
NO2
SO2Na
H
N
PhNH2 1.2 equiv
N
N
N
NO2
NaH, 1.2 equiv
DMF, rt, 10 h
O
MIL-101(Fe), NaHSO3
DMSO/H2O, 60 oC, 24 h
PhHN
Cl
4,
5
76%
, 79%
4-ClC6H4SH 1.2 equiv
K2CO3 1.2 equiv
F
Cl
SO2Na
S
Cl
S
H
O
S
N
NO2
MIL-101(Fe), NaHSO3
DMSO/H2O, 60 oC, 24 h
2 wt.% TX100/H2O
50 oC, 10 h
NO2
O
, 83%
6
7
, 83%
Cl
OBn
(1) NaOH 1.2 equiv
EtOH, rt, 1 h
OH
OBn
H
O
S
N
Ph SO2Na
NO2
NO2
(2) BnBr 1.2 equiv
DMF, rt, 10 h
MIL-101(Fe) NaHSO3
DMSO/H2O, 60 oC, 24 h
O
N
N
N
8
9
, 84%
, 75%
Scheme 3. Synthesis of N-arylsulfonamides 5, 7 and 9. Reagents and conditions: nitroarene (0.25 mmol), sodium arylsulfinate (0.5 mmol),
MIL-101(Fe) (5 mg, 8 mol% of Fe), NaHSO3 (0.5 mmol), DMSO/H2O (v/v =1:1, 1 mL), 60 °C, 24 h; isolated yield.
MIL-101(Fe)
O
H
Na2SO3, NaHCO3
H2O, 80 oC, 20 h
Ar NO2
+
Ar' SO2Cl
Ar
N
S
Ar'
O
O
O
S
H
H
S
N
N
Cl
O
, 85%
O
3b
3a
3c
, 77%
F
H2N
O
H
O
S
N
H
S
N
N
O
, 82%
O
, 65%
3e
CF3
O
S
O
H
N
H
OMe
S
N
O
3g
O
3f
, 74%
, 53%
O
S
O
H
N
H
HN
O
Cl
S
N
O
O
3m
, 86%
3p
, 75%

Scheme 4. Reactions of nitroarenes with arylsulfonyl chlorides in water. Reagents and conditions: arylsulfonyl chloride (1.0 mmol), nitroarene
(0.5 mmol), Na2SO3 (1.0 mmol), NaHCO3 (1.0 mmol), MIL-101(Fe) (10 mg, 8 mol% of Fe), H2O (2 mL), 80 °C, 20 h; isolated yield.
100
80
60
40
20
0
0
1
2
3
4
5
6
run
Figure 1. Recycling studies. Reagents and conditions: 1a (5 mmol), 2a (10 mmol), NaHSO3 (10 mmol), MIL-101(Fe) (100 mg, 8 mol% of Fe),
H2O (20 mL), 60 °C, 24 h; isolated yield.
Sodium arylsulfinates were also synthesized using arylsulfonate chlorides as the starting materials. The reactions proceeded smoothly
in the presence of Na2SO3 and NaHCO3 using MIL-101(Fe) as the catalyst, and eight N-arylsulfonamides were obtained with moderate
to good yields (Scheme 4).
Finally, investigations were also conducted to assess the potential for recycling the catalytic system using the reaction of 1a and 2a.
The model reaction was also scaled up to 5 mmol (gram-scale) to demonstrate the possibility for large-scale operation. After reaction
completion, EtOAc was added to the reaction mixture, which was centrifuged to separate MIL-101(Fe) from the organic phase. Then,
the product containing organic phase was separated by extraction, and the aqueous phase containing MIL-101(Fe) was used directly in
the next run. The process can be repeated 6 times without an obvious change in yield (Fig. 1).
MIL-101(Fe)
NaHSO3
NO2
1a
SO2Na
NH2
(1)
H2O, 60 oC, 12 h
10
, 31%
MIL-101(Fe)
NaHSO3
H2O, 60 oC, 12 h
+
SO2NHPh (2)
3a
PhNHOH
2a
, 15%
MIL-101(Fe)
NaHSO3
H2O, 60 oC, 12 h
SO2Na
+
PhNH2
10
no reaction
(3)
(4)
2a
SO2Cl
+
MIL-101(Fe)
PhNHOH
SO2NHPh
NaHCO3. Na2SO3
H2O, 80 oC, 20 h
3a
, 79%
SO2Cl
+
MIL-101(Fe)
PhNH2
(5)
(6)
SO2NHPh
3a
NaHCO3. Na2SO3
H2O, 80 oC, 20 h
10
, 65%
SO2Cl
SO2Na
MIL-101(Fe)
NaHCO3. Na2SO3
H2O, 80 oC, 20 h
2a,
95%
Scheme 5. Control experiments.
Cl
O
O
O
O
Fe
O
O
O
O
O
Fe(III)
Fe
Fe
H2O
OH2
O
O
O
O
MIL-101(Fe)
SBU
-
ArSO2
O
Fe(III)
2
HO
N
S
O
2-
Ar' Ar
SO4
O
D
Fe(III)
A
-
Ar
S
O
HSO3
-
HSO3
Ar'NO2
1
O
S
Fe(III)
Fe(III)
O
O
S
Ar
A'
O
-
O-
N
O
HSO4
O
Ar' N+
Fe(III)
Ar'
Ar
O
Ar'NHSO2Ar
B
C
3
Figure 2. Tentative pathway for the MIL-101(Fe)-catalyzed reaction of nitroarenes and sodium arylsulfinate.

Several control experiments were performed to investigate the reaction pathway (Scheme 5). Aniline 10 was obtained in 35% yield
when only nitrobenzene 1a was employed under the optimized reaction conditions (eq. 1). The reaction of 2a and N-
phenylhydroxylamine resulted in a poor yield of 3a, while no reaction occurred in the reaction of 2a and 10 (eq. 2 and 3). In the case of
4-methylbenzene sulfonyl chloride, both 10 and N-phenylhydroxylamine reacted to yield product 3a with moderate yields (eq. 4 and 5).
4-Methylbenzene sulfonyl chloride could also be reduced to 2a under the same conditions (eq. 6). According to these results, it can be
concluded that (1) both nitrobenzene and 4-methylbenzene sulfonyl chloride could be reduced to aniline and 2a, respectively, under the
optimized conditions; (2) aniline and N-phenylhydroxylamine are not intermediates in the reaction of 1a and 2a; (3) aniline and N-
phenylhydroxylamine may be intermediates in the reaction of 1a and 4-methylbenzene sulfonyl chloride.
Based on the results of previous reports and control experiments,6,14 the Fe(III) in the secondary building units (SBU) of MIL-101(Fe)
should be the active site for the reaction (Fig. 2). All three iron sites in SBU may be active sites for the reaction. The two iron sites
coordinated with water can activate nitroarenes by coordination. The iron site bonded with chloride can activate both nitroarenes and
sodium arylsulfinates via coordination and electrostatic interactions. Compared with iron salts, the Fe(III) in MIL-101(Fe) is more
stable and has stronger Lewis acidity owing to the SBU structure.
A proposed mechanism is illustrated in Figure 2 according to the literature and experimental results.6 First, the iron arylsulfinate A
(or A’) is formed through electrostatic interactions between Fe(III) and the arylsulfinate, in which the sulfur atom is more nucleophilic
than it is in 2 owing to weaker electrostatic interactions between Fe(III) and the arylsulfinate. Meanwhile, the nitro group of 1 can be
activated by coordination and electrostatic interactions with iron to form C, in which the nitrogen atom is more electrophilic than it is in
1. Then, complexation and nucleophilic substitution of A’ to the nitrogen atom of C results in intermediate B, which is attacked by
2-
bisulfite to afford intermediate D, releasing Fe(III) and SO4 . The final product 3 is formed following the reduction of intermediate D
by bisulfite.
3. Conclusions
In summary, a MIL-101(Fe)-catalyzed coupling between nitroarenes and sodium arylsulfinates or arylsulfonyl chlorides has been
developed for the synthesis of N-arylsulfonamides. The protocol processes several advantages including the use of a recyclable catalytic
system, high chemoselectivity and high yields.
4. Acknowledgements
We gratefully acknowledge the Chinese Postdoctoral Science Foundation (2015M571761, 2016T90465). We thank Lan Yi at Test
Center Nanjing University of Science and Technology for the help in obtaining the NMR data.
Supplementary Material
Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.tetlet.2018.xxx.
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Highlights:
(i) A new iron catalytic system for the couplings of arylsulfinates with nitroarenes
(ii) Excellent chemoselectivity even in cases of nitroarenes with reactive groups
(iii) The use of recyclable and green catalytic system