Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides

Article abstract of DOI:10.1055/s-0040-1707310

A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO ₂·CH ₂O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing-coupling pathway.

Full text of DOI:10.1055/s-0040-1707310

SYNLETT
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart
2021, 32, 81–85
letter
81
en
G. Zhang et al.
Letter
Synlett
Dual Roles of Rongalite: Reductive Coupling Reaction to Construct
Thiosulfonates Using Sulfonyl Hydrazides
Guofu Zhanga
Qiankun Fana
Yiyong Zhaob
Huimin Wanga
Chengrong Ding*a
O
S
NHNH2
O
S
R
benzotrifluoride
NaHSO2•CH2O
80 °C, air, 5 h
O
R
S
R
O
19 examples
up to 91% yield
R = alkyl, aryl
0
0
0
0
-0
0
0
1
-
6
0
0
0
-
3
9
6
5
transition-metal-free
operational simplicity
without any toxic byproducts
reduction–coupling pathway
a College of Chemical Engineering, Zhejiang University of
Technology, Hangzhou 310014, P. R. of China
gfzhang@zjut.edu.cn
dingcr@zjut.edu.cn
b Zhejiang Ecological Environment Low Carbon Development
Center, Hangzhou 310012, P. R. of China
Corresponding Author
Received: 21.07.2020
Accepted after revision: 04.09.2020
Published online: 09.10.2020
halides with alkali-metal thiosulfonates,7 and coupling of
alkali-metal sulfinates with disulfides by means of a pro-
moter to activate the sulfur–sulfur bond.8 Unfortunately,
many of these methods encounter several blemishes, such
as to require the use of transition metals or stoichiometric
amounts of oxidants, toxic reagents, harsh reaction condi-
tions, or limited substrate scope, etc.9
Sulfonyl hydrazides, easily accessible and stable solids,
were diffusely used as convenient sulfur nucleophiles or
electrophiles in organic synthesis.10 In 1972, Meier and co-
workers first reported the preparation of thiosulfonates via
thermal decomposition of arenesulfonyl hydrazides, upon
heating above their melting point (Scheme 1a).11 Guo uti-
lized a catalytic system based on Pd/ZrO2 nanocomposite
photocatalyst to obtain thiosulfonates in moderate to good
yield (Scheme 1b).12 Another approach discovered by the
group of Wei delivers thiosulfonates in high yields in the
presence of NIS/K2S2O8/THF at 70 °C (Scheme 1c).13 Very re-
cently, Kim et al. developed the CuCl2-promoted decompo-
sition of sulfonyl hydrazides to access diverse symmetrical
thiosulfonates with various functional groups (Scheme
1d).14
DOI: 10.1055/s-0040-1707310; Art ID: ss-2016-n0277-op
Abstract A tunable and practical transformation of structurally di-
verse sulfonyl hydrazides into thiosulfonates in the presence of Ron-
galite (NaHSO2·CH2O) was developed. Transition-metal-free conditions,
operational simplicity, and readily available reagents are the striking
features of this protocol. It is the first example for the synthesis of thio-
sulfonates using sulfonyl hydrazides with the assistance of reductant.
Additionally, the mechanistic studies revealed that this transformation
probably undergoes via a reducing–coupling pathway.
Key words sulfonyl hydrazides, Rongalite, thiosulfonates, transition-
metal-free, reductive coupling
Sulfur-containing organic compounds, due to their
unique properties, are widely used in material, medicinal,
agrochemical applications, and other fields.1 Notably, thio-
sulfonates have attracted significant attention for their ex-
pressions of a broad spectrum of clinical and pharmaceuti-
cal properties, including antimicrobial, antifungal, and anti-
viral agents.2 Besides, thiosulfonate derivatives have shown
widespread applications in both polymer production and
photographic processes.3 Moreover, they are powerful elec-
trophilic sulfenylating agents in synthetic organic chemis-
try because of their superior reactivity and stability.4 In the
light of the aforementioned applications, preparation of the
thiosulfonate derivatives has been pursued for a long time
by researchers.
Initially, the most practically methods for the synthesis
of symmetrical thiosulfonates were the direct oxidation of
disulfides, thiosulfinates, or thiols via various oxidants.5
Another common protocol was based on the reductive di-
merization of sulfonyl chlorides or coupling with thiols to
synthesize symmetrical/unsymmetrical thiosulfonates.6
Besides, an alternative approach for the synthesis of thio-
sulfonates comprised a nucleophilic substitution of alkyl
O
S
R
S
(a)
(b)
(c)
(d)
(e)
neat, air, 8–30 h
above mp
O
R
O
O
O
R
R
R
S
S
S
S
Pd/ZrO2, EtOH, O2
visible light, 45 °C, 24 h
O
R
R
R
O
S
NHNH2
S
NIS, K2S2O8
THF, 70 °C, 8 h
O
R
O
S
CuCl2 (10 mol%)
toluene, 90 °C, N2, 15 h
O
O
R
S
benzotrifluoride
NaHSO2·CH2O
80 °C, air, 5 h
S
O
R
This work
Scheme 1 Synthesis of thiosulfonates using sulfonyl hydrazides
© 2020. Thieme. All rights reserved. Synlett 2021, 32, 81–85
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

82
G. Zhang et al.
Letter
Synlett
To the best of our knowledge, synthesis of thiosulfon-
ates using sulfonyl hydrazides with the assistance of reduc-
tant has not been explored. Herein, we report a tunable and
practical transformation of structurally diverse sulfonyl hy-
drazides into thiosulfonates in the presence of Rongalite as
reductant (Scheme 1e).
Initial optimization of the reaction was performed with
4-methylbenzenesulfonohydrazide (1a) as a model sub-
strate (Table 1). When the reaction mixture of 1a (0.2
mmol) and NaHSO2·CH2O (0.2 mmol) in EtOH (2.0 mL) was
stirred at 80 °C under air for 5 h, only 13% yield of the de-
sired 4-methylbenzenesulfonothioate (2a) product was iso-
lated (entry 1). Encouraged by this initial result, we per-
formed a further screening of the reaction conditions with
respect to the reductant. The examination indicated that
the performance of NaHSO2·CH2O was superior to that of
other reductants (entries 1–5). It was noteworthy that ethyl
4-methylbenzenesulfinate was isolated when the reaction
used NaHSO3 as reductant (entry 5). Control experiment
confirmed that reductant was essential for the transforma-
tion to proceed (entry 6). Among the examined solvents,
such as CHCl3, toluene, CH3CN, ethyl acetate and benzene,
benzotrifluoride exhibited the highest efficiency in this
transformation (entries 7–13). Intriguingly, the efficiency
of this transformation was significantly affected by the po-
larity of solvents, and the weak polarity solvent is superior
to the strong polarity. A yield of 86% was achieved after in-
creasing the amount of NaHSO2·CH2O to 2.0 equiv, while a
further increase in NaHSO2·CH2O quantity decreased the
yield (entries 14 and 15). The output was also strongly gov-
erned by the reaction temperature; the yield decreased sig-
nificantly upon lowering (60 °C) as well as increasing (100
°C) the reaction temperature (entries 18 and 19).
Table 1 Optimization of Reaction Conditions
O
S
NHNH2
O
reductant, solvent
atmosphere, temp, time
O
S
S
O
1a
2a
(0.2 mmol)
Entry
Reductant
mmol
Solvent
mL
Temp (°C)
Atmosphere Time (h)
Isolated yield (%)
1
2
NaHSO2·CH2O
Na2SO3
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
2.0
4.0
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
CHCl3
toluene
EtOAc
CH3CN
THF
2.0
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
60
100
80
80
80
80
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
air
N2
O2
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
3
7
5
5
5
5
5
5
13
<5
trace
<5
81
0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.0
3.0
2.0
2.0
3
Na2S2O3·5H2O
Na2S2O4
4
5a
6
NaHSO3
–
7
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
NaHSO2·CH2O
60
75
47
48
54
82
73
86
67
77
86
72
75
91
73
87
83
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
benzotrifluoride
benzene
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
benzotrifluoride
a Product was the ethyl 4-methylbenzenesulfinate.
© 2020. Thieme. All rights reserved. Synlett 2021, 32, 81–85

83
G. Zhang et al.
Letter
Synlett
With the increase of solvent volume, poor yields of 2a
were observed, but a decrease of the solvent volume could
give the target product in 91% yield (Table 1, entries 20 and
21). A decreased yield was obtained when the reaction was
carried out under N2 or O2 (entries 22 and 23). Therefore,
the optimal reaction conditions were found to include 4-
methylbenzenesulfonohydrazide (1a, 0.2 mmol), NaH-
SO2·CH2O (2.0 equiv) in benzotrifluoride (1.0 mL) at 80 °C
under air for 5 h.
With the optimized reaction conditions in hand, we
next probed the substrate scope of the present protocol
(Scheme 2). With respect to arenesulfonyl hydrazides, a
wide range of functionalities substituted on the benzene
ring was compatible with the present reductive coupling
reaction, including alkyl, fluoro, chloro, methoxy, trifluoro-
methyl, and trifluoromethoxy. Hence, a series of novel thio-
sulfonates were readily accessed in yields ranging from
moderate to good (2a–p, 52–91%). 4-Methylbenzenesul-
fonohydrazide (1a) exhibited the highest reactivity to af-
ford the corresponding 4-methylbenzenesulfonothioate
(2a) in 91% yield. For methyl-substituted arenesulfonyl hy-
drazides, though the position or number of methyl is differ-
ent, all work well under standard reaction conditions, giv-
ing the target products in good to excellent yields (2a,i,k,p).
Moreover, polycyclic aromatic sulfonyl hydrazides proved
to be suitable reactants, affording 2n and 2o in moderate
yields.
It was worth noting that the reduction of arenesulfonyl
hydrazides with o-Cl, o-Br, and thiophene-2-sulfonohydra-
zide 1s produced the corresponding disulfides instead. We
suspected that the corresponding thiosulfonates were easi-
ly further reduced to disulfides by the Rongalite. To our dis-
appointment, the reduction of phenylmethanesulfonohy-
drazide 1t did not proceed well.
To gain insight into the mechanism of this transforma-
tion, a series of preliminary experiments were performed.
When 2.0 equiv of 2, 4-di-tert-butyl-4-methylphenol (BHT)
was introduced under the standard reaction conditions, the
yield of 2a was not significantly affected, which points
away from a radical pathway (Scheme 3A). Apparently, the
reductant was essential for this reaction, as the reaction
without reductant participation only generated small
amounts of the desired product (13% yields for 2a). The re-
action was completely suppressed when the radical scaven-
gers 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and
BHT were added in the reaction conditions without reduc-
tant, suggesting that a radical pathway might be the minor
process in this reaction (Scheme 3B). Besides, the reaction
under N2 atmosphere was found to be uninfluenced, lead-
ing to excellent yield (87% yield for 2a, Scheme 3C). On the
basis of the relevant literature reports,15 we speculated that
the 4-methylbenzenesulfinic acid or sodium 4-methylben-
zenesulfinate might be an intermediate for this reaction.
Subsequently, two crucial control experiments were per-
formed to further study the reaction mechanism. 4-Methyl-
O
S
benzotrifluoride
NaHSO2•CH2O
80 °C, air, 5 h
NHNH2
O
R
O
R
S
S
R
O
1
2
O
S
O
S
S
O
O
S
O
S
S
S
S
O
O
O
O
O
2a, 91%
2b, 63%a
2c, 73%
2d, 74%
2e, 68%
CF3
O
S
S
O
S
O
S
S
O
O
S
S
O
O
S
S
S
O
2h, 66%
O
O
O
F3C
F3C
F
Cl
F
Cl
CF3
CF3
CF3
2f, 52%b
2j, 76%b
2g, 55%
2i, 63%
O
S
O
S
O
S
S
O
S
S
S
S
S
S
O
O
O
O
O
F
F
2k, 82%
2l, 68%
2m, 80%
2n, 63%
2o, 87%
Cl
O
S
Br
S
O
S
S
S
S
S
S
S
S
S
O
S
O
Br
Cl
2p, 82%
2q, 65%
2r, 60%
2s, 69%
2t, 0%
Scheme 2 Scope of the synthesis of the thiosulfonates. Reagents and conditions: Arenesulfonyl hydrazide 1 (0.2 mmol), NaHSO2·CH2O (2.0 equiv),
benzotrifluoride (1.0 mL) at 80 °C under air for 5 h. Isolated yield. a Toluene (1.0 mL). b Arenesulfonyl hydrazides 1 (0.4 mmol).
© 2020. Thieme. All rights reserved. Synlett 2021, 32, 81–85

84
G. Zhang et al.
Letter
Synlett
benzenesulfinic acid, instead of 4-methylbenzenesulfono-
hydrazide (1a), was used to react with Rongalite under the
standard reaction conditions, and afforded the target prod-
uct 2a in 69% yield, which demonstrated that 4-methylben-
zenesulfinic acid might be an intermediate for this reaction
(Scheme 3D). However, no desired product 2a was obtained
in this reaction, when sodium 4-methylbenzenesulfinate
with Rongalite was reacted under the same standard reac-
tion conditions (Scheme 3E).
O
S
O
S
S
NHNH2
O
O
1a
2a
HO
SO2Na
coupling
A
O
S
S
NH
N
E
SO2Na
O
A
reduction
HO
SO2Na
Δ
O
O
S
S
OH
O
S
O
S
standard conditions
BHT (2 equiv)
H+
NH NH2
O
D
S
(A)
B
O
S
O
O
O
2a, 74%
C
O
O
S
benzotrifluoride
80 °C, air, 5 h
S
S
(B)
NH NH2
Scheme 4 Proposed mechanism
O
O
2a, 13%
Yield of 2a
Additive
possible reaction mechanism was proposed to explicate the
product formation. Further studies on this original ap-
proach are ongoing in our laboratory.
TEMPO (2.0 equiv)
BHT (2.0 equiv)
<5%
0
O
O
S
benzotrifluoride
NaHSO2•CH2O
80 °C, N2, 5 h
S
S
(C)
NH NH2
O
O
Funding Information
2a, 87%
We acknowledge financial support from the National Natural Science
Foundation of China (20702051), the Natural Science Foundation of
O
S
O
standard conditions
standard conditions
OH
S
S
(D)
(E)
Zhejiang Province (LY13B020017).
N
aturalSc
i
e
nc
e
F
o
u
n
d
a
ti
o
n
o
f
Z
h
e
ji
a
n
g
Pro
v
i
nce(
L
Y
1
3
B
0
2
0
0
1
7)
N
a
ti
o
na
l
N
a
t
ura
l
S
c
i
e
n
c
e
F
o
u
n
dati
o
n
o
f
C
h
i
na(
2
0
7
0
2
0
5
1
)
O
2a, 69%
O
S
O
Supporting Information
ONa
S
S
O
Supporting information for this article is available online at
2a, 0%
https://doi.org/10.1055/s-0040-1707310.
S
u
p
p
orti
n
gI
n
f
orm
a
ti
o
n
S
u
p
p
orti
n
gInform
a
ti
o
n
Scheme 3 Controlled experiments for mechanism study
References and Notes
On the basis of previous reports and the results of the
control experiments,11–14,16 we try to postulate a probable
mechanism as shown in Scheme 4. Initially, intermediate A
was generated by the reaction of 4-methylbenzenesulfono-
hydrazide (1a) with NaHSO2·CH2O. Subsequently, interme-
diate A underwent thermal decomposition to afford sulfinyl
anion B, which can resonate with the sulfur-centered anion
C.17 Next, species C is trapped by H+ to form key intermedi-
ate sulfinic acid D, which was further reduced to thiolate E
by NaHSO2·CH2O. Finally, nucleophilic substitution reaction
of thiolate E with intermediate A occurred to attain target
product 2a.
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Letter
Synlett
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A mixture of 1a (0.2 mmol), NaHSO2·CH2O (0.4 mmol, 47.2 mg),
and benzotrifluoride (1.0 mL) in a 15 mL flask was heated at 80
°C under air for 5 h. The reaction mixture was cooled to room
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(20 mL). The organic layers were dried over anhydrous Na2SO4,
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1H NMR (500 MHz, CDCl3):  = 7.47 (d, J = 8.3 Hz, 2 H), 7.29–7.20
(m, 4 H), 7.15 (d, J = 8.0 Hz, 2 H), 2.43 (s, 3 H), 2.39 (s, 3 H).13
C
NMR (126 MHz, CDCl3):  = 144.56, 142.01, 140.43, 136.45,
130.17, 129.33, 127.56, 124.56, 124.56, 21.63, 21.45. HRMS (EI-
TOF): m/z calcd for C14H14O2S2: 278.0435; found: 278.0466.
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