A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the synthesis of sulfones

Article abstract of DOI:10.1016/j.tetlet.2020.151975

A practical and efficient approach adopting transition-metal-free cross-coupling of sulfonyl hydrazides with benzyl ammonium salts has been developed to synthesize benzyl sulfones using Cs₂CO₃ as base under mild conditions. The protocol employs stable and easy to handle coupling partners, and is endowed with good substrate compatibility, leading to functional benzyl sulfones in good yields.

Full text of DOI:10.1016/j.tetlet.2020.151975

Tetrahedron Letters xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
A general and practical sulfonylation of benzylic ammonium salts
with sulfonyl hydrazides for the synthesis of sulfones
⇑
⇑
⇑
Haibo Zhu , Yingying Zhang, Yishuai Liu, Liu Yang, Zongbo Xie , Guofang Jiang, Zhang-Gao Le
School of Chemistry, Biology and Material Science, East China University of Technology, Nanchang 330013, Jiangxi, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A practical and efficient approach adopting transition-metal-free cross-coupling of sulfonyl hydrazides
with benzyl ammonium salts has been developed to synthesize benzyl sulfones using Cs2CO3 as base
under mild conditions. The protocol employs stable and easy to handle coupling partners, and is endowed
with good substrate compatibility, leading to functional benzyl sulfones in good yields.
Ó 2020 Elsevier Ltd. All rights reserved.
Received 14 March 2020
Revised 20 April 2020
Accepted 24 April 2020
Available online xxxx
Keywords:
Sulfones
CAN cleavage
CAS formation
Transition-metal-free
Introduction
In recent years, the readily available arylsulfonyl hydrazides
have attracted considerable attention in organic synthesis as pow-
The formation of CAS bonds has emerged as of great interest
over the years in organic synthesis due to their prevalence in many
biologically active compounds including pharmaceuticals and
organic materials [1]. As types of these species, sulfone-containing
compounds often show different biological activities and provide
important functions in applications in the pharmaceutical industry
[2]. Tremendous efforts have been devoted to develop novel and
efficient methodologies to construct sulfones during past decades
[3], such as the oxidation of the corresponding sulfides [4], the
electrophilic aromatic substitution of arenes [5], the coupling reac-
tion of arylboronic acids [6]. With the development of organic syn-
thesis, rapid progress has been witnessed with the insertion of
sulfur dioxide by using inorganic sulfites or the sulfur dioxide sur-
rogate of 1,4-diazabicyclo[2.2.2]octane-sulfur dioxide [DABSO:
DABCO-bis(sulfur dioxide)] as the source [7]. Our group have also
reported N-heterocyclic carbene metal-catalyzed sulfonylations
towards the synthesis of sulfones from boronic acids with various
electrophiles under mild conditions, such as alkyl halides and
diaryliodonium salts [8]. However, fewer synthetic steps, less toxic
waste, high selectivity and milder conditions in the formation of
sulfone increasingly become a research hotspot in the future
organic synthesis.
erful sulfonyl source [9] and arylation reagents [10] via SAN bond
cleavage in the transition-metal catalyzed reactions [11]. Com-
pared to other sulfenylation/sulfonation agents [12], arylsulfonyl
hydrazides are insensitive to air and moisture due to stability
and easy preparation, more significantly, H2O and N2 are the only
byproducts. However, the noble and toxic transition-metals resi-
due which difficult to separate from the system, greatly restricts
the practicality of these approaches (Scheme 1a).
Remarkably, few examples include the transition metal-free
mediated sulfonylation in the presence of equivalent of oxidant
and elemental iodine (Scheme 1b, 1c), which violate the concept
of green chemistry [13]. Therefore, it remains highly desirable to
develop more general and straightforward methods for the facile
preparation of sulfones, without transition-metal catalysts or
oxidants.
Due to the higher CAN reactivity and convenient preparation,
the quaternary ammonium salts have represented types of novel
electrophilic reagents and attracted lots of attention in organic
synthesis [14], especially in the construction of CAC and CAS
bonds catalyzed by transition-metal with various nucleophilic
reagents [15,16]. However, leveraging recent remarkable achieve-
ments in uncovering practical synthetic reactions that relied on
transition-metal-free approaches [17], it is particularly appealing
to explore the potential applications in designing and identifying
useful alternatives to constructed various of C-X bonds. To the best
of our knowledge, the CAS bond formation through SAN and CAN
cleavage by using benzylic ammonium salts and arylsulfonyl
⇑
Corresponding authors.
E-mail addresses: hbzhu@ecut.edu.cn (H. Zhu), zbxie@ecut.edu.cn (Z. Xie),
zhgle@ecut.edu.cn (Z.-G. Le).
https://doi.org/10.1016/j.tetlet.2020.151975
0040-4039/Ó 2020 Elsevier Ltd. All rights reserved.
Please cite this article as: H. Zhu, Y. Zhang, Y. Liu et al., A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the
synthesis of sulfones, Tetrahedron Letters, https://doi.org/10.1016/j.tetlet.2020.151975

2
H. Zhu et al. / Tetrahedron Letters xxx (xxxx) xxx
Table 1
Optimization of reaction conditions.a
Entry
Base
Solvent
3a (%)b
1
2
3
4
5
6
7
8
K2CO3
Na2CO3
tBuOK
K3PO3
CsF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DCE
Dioxane
DMSO
DMAc
NMP
77
76
56
56
52
80
32
trace
68
66
75
82
Cs2CO3
/
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
9
10
11
12c
a
Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol, 1.0 equiv), base (1.0 equiv) in
2 mL solvent at 120 °C under an atmosphere of N2 for 24 h.
b
Isolated yield.
1.5 equiv of Cs2CO3 was used.
c
Scheme 1. Various synthetic routes to sulfonyl-containing compounds.
ammonium iodides as depicted in Table 2. Both benzylic ammo-
nium iodides with electron-withdrawing and electron-donating
groups attached on the phenyl ring were compatible in this process
(3b-3g). The relative position of methyl located on the aromatic
ring of benzylic ammonium iodides had slightly influence on the
efficiency of the transformation, and considerable yields were
obtained with ortho-, and meta-substituents (3b-3c), only 48% pro-
duct 3d was detected when para-isomer was used as coupling
partner. Unexpectedly, steric hindered substrate, such as bulky 1-
naphthylbenzylic ammonium salt and 2-naphthylbenzylic ammo-
hydrazides has not been explored so far. Herein, we would like to
explore the possibility of direct sulfonylation of benzylic ammo-
nium salts to build arylsulfones promoted by cesium carbonate
under transition-metal-free conditions (Scheme 1d).
Results and discussion
With p-toluenesulfonyl hydrazide (1a) and benzylic ammonium
iodides (2a) as the model substrates, we started the optimization
using K2CO3 as base in N,N-dimethylformamide (DMF) at 120 °C
for 24 h, To our delight, this reaction takes place in the absence
of any transition metal catalyst, product 3a could be isolated in
77% yield (Table 1, entry 1). Similar outcome was obtained when
Na2CO3 was applied (Table 1, entry 2). No further enhancement
was found when other bases (including strong base tBuOK,
K3PO4, and CsF) were used instead (Table 1, entries 3, 4 and 5).
Delightedly the yield was improved to 80% when Cs2CO3 was used
(Table 1, entry 6). Remarkably, When the reaction was performed
in the absence of Cs2CO3, only 32% yield was found. (Table 1, entry
7). Merely trace yield was found when dichloroethane (DCE) was
used (Table 1, entry 8) as the solvent of this coupling, and the infe-
rior yields were found when dioxane, dimethyl sulfoxide (DMSO)
and N,N-dimethylacetamide (DMAc) (Table 1, entries 9, 10 and
11) were used. After intensive optimization of the other solvents
and bases (for more information see the ESI, Table S1), good result
was found when N-methylpyrrolidone (NMP) and Cs2CO3 were uti-
lized, and product 3a was formed in 82% yield (Table 1, entry 12),
probably due to better solubility of substrates in amide solvents. In
order to further investigate the effects of this approach, the reac-
tion temperature and molar ratio were also considered (for more
information see the ESI, Table S2). Finally, a yield of 82% was pro-
vided when using 1.5 equiv of Cs2CO3, 2.0 equiv of p-toluenesul-
fonyl hydrazide (1a) and 1.0 equiv of benzylic ammonium iodide
(2a) in 2 mL NMP at 120 °C under an atmosphere of N2 for 24 h.
In addition, the nature of the counterion had negative influence
on the reaction, and variable yields were obtained (for more infor-
mation see the ESI, Table S3).
Table 2
Reaction of arylsulfonyl hydrazides (1) with various benzylic ammonium iodides (2).a
Upon the identification of optimal reaction conditions, a series
of alkyl sulfones was obtained in moderate to good yields from
arylsulfonyl hydrazides with a variety of substituted benzylic
a Reaction conditions: 1 (0.4 mmol), 2 (0.2 mmol, 1.0 equiv), Cs2CO3 (1.5 equiv) in 2
mL NMP at 120 °C under an atmosphere of N2 for 24 h.
b
Isolated yield.
Please cite this article as: H. Zhu, Y. Zhang, Y. Liu et al., A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the
synthesis of sulfones, Tetrahedron Letters, https://doi.org/10.1016/j.tetlet.2020.151975

H. Zhu et al. / Tetrahedron Letters xxx (xxxx) xxx
3
nium gave out the excellent result in this reaction (3l and 3n, 82
and 79%, respectively), and the ideal yields were observed when
p-trifluoromethyl benzene sulfonyhydrazide instead of benzene-
sulfonyl hydrazide (3m and 3o, 92 and 96%, respectively). Similar
outcome was obtained when a range of ortho-substitutes even
with strong electron-donating and electron-withdrawing were
used on the coupling process, up to 82% yields were afforded (3k,
3s, and 3h-3j). The process works well for substrates displaying
(hetero)aryl ammonium salt, and good results were observed with
the couplings of 2-furyl and 2-thienyl benzylic ammoniums as sub-
strates (3p, 3q), which clearly indicated the protocol efficiency.
Based on the optimization study, the scope of the arylsulfonyl
hydrazides was also studied, the results are summarized in Table 3.
To our delight, arylsulfonyl hydrazides bearing strong electron-
donating and strong electron-withdrawing substituents on the
aromatic ring were all tolerated (4a-4l). The arylsulfonyl hydra-
zides with strong electron donor groups including tert-butyl and
methoxy had well compatibilities, and good yields were produced
in synthetically (4b and 4c, 76 and 67%, respectively). Unexpect-
edly, the reaction with electron-poor sulfinate was well tolerated,
84% and 92% yields of products 4e and 4f were obtained even with
strong electron-withdrawing groups (trifluoromethyl), and the
lower results were shown in 4g and 4h when the sensitive func-
tional groups including chloro and bromo were used. The steric
effect of arylsulfonyl hydrazides had a certain effect on the effi-
ciency of this transformation. Only acceptable yields were
observed when the large steric effect arylsulfonyl hydrazides were
applied (4d and 4j). Notably, 2,3-dihydrobenzofuransulfonyl
hydrazide could work well in the reaction to provide the corre-
sponding heterocyclic products 4k and 4m in 56% and 73% yields.
In order to stress the practicality of this protocol, a gram-scale
reaction between p-toluenesulfonyl hydrazide (1a) and benzylic
ammonium iodides (2a) was carried out (Scheme 2). When
8.0 mmol of 2a reacted with TsNHNH2 under the optimal condi-
tions, the reaction also proceeded well to give the corresponding
product 3a with a satisfactory yield of 78%, demonstrated the high
efficiency of the newly developed sulfones protocol.
To gain an insight into the reaction mechanism, the following
control experiments were conducted to better understand the pos-
sible mechanism of this coupling reaction (Scheme 3). When the
radical inhibitor TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy)
was added to the reaction under optimized reaction conditions,
and 67% of desired product 3a was obtained (Scheme 3, eq 1), indi-
cating that a radical reaction might not be involved in the reaction.
Furthermore, no radical intermediate was trapped when 1,1-
diphenylethylene was employed in the reaction, and 75% of 3a
was gained (Scheme 3, eq 2). 3a could also be obtained in 56% yield
when p-toluenesulfinate (7a) was used as the substrate instead of
1a under the standard conditions (Scheme 3, eq 3). However,
TEMPO was found to have little influence on this reaction. We
observed that reaction of 2a with Cs2CO3 in the presence of NMP
at 120 °C generates benzyl iodide 7b in 52% isolated yield
(Scheme 3, eq 4). The results implied that aryl sulfinate and benzyl
iodide maybe intermediates in this process.
On the basis of these results and previous works [13], a possible
mechanism for the cross-coupling reaction is proposed in
Scheme 4. The sulfonyl nucleophile intermediate A was generated
from base-accelerated decomposition of benzenesulfonohydrazide
[12a]. Then benzyl iodide B was produced by heating benzylic
ammonium iodide releasing a molecule of trimethylamine simul-
taneously [18]. Lastly, nucleophilic substitution takes place in sol-
vent between sulfonyl nucleophile and benzyl iodide to afford the
desired product. More detailed mechanistic studies of this reaction
are ongoing in our laboratory.
Conclusions
In summary, for the first time, the sulfonylaiton of benzylic
ammonium salts using arylsulfonyl hydrazides as sulfonylation
reagents in absence of transition-metal has been developed for
Table 3
Reaction of benzylic ammonium iodide (2) with various arylsulfonyl hydrazides (1).a
Scheme 2. Gram-scale synthesis of 3a.
a Reaction conditions: 1 (0.4 mmol), 2 (0.2 mmol, 1.0 equiv), Cs2CO3 (1.5 equiv) in 2
mL NMP at 120 °C under an atmosphere of N2 for 24 h.
b
Isolated yield.
Scheme 3. Control experiments for the reaction mechanism.
Please cite this article as: H. Zhu, Y. Zhang, Y. Liu et al., A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the
synthesis of sulfones, Tetrahedron Letters, https://doi.org/10.1016/j.tetlet.2020.151975

4
H. Zhu et al. / Tetrahedron Letters xxx (xxxx) xxx
Province (20192BAB213006, 20181BBH80007), Youth Foundation
of Jiangxi Educational Committee (GJJ170460), East China Univer-
sity of Technology Research Foundation for Advanced Talents
(No. DHBK2017168) and School of Chemistry, Biology and Material
Science at East China University of Technology is gratefully
acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tetlet.2020.151975.
Scheme 4. Proposed reaction mechanisms.
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Please cite this article as: H. Zhu, Y. Zhang, Y. Liu et al., A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the
synthesis of sulfones, Tetrahedron Letters, https://doi.org/10.1016/j.tetlet.2020.151975