PhI(OAc)2-mediated decomposition of N-arylsulfonyl hydrazones: metal-free synthesis of (E)-vinyl sulfones

Article abstract of DOI:10.1016/j.tetlet.2016.07.099

A novel and efficient approach for the preparing of (E)-vinyl sulfones via PhI(OAc)₂-mediated decomposition of ketone-derived N-arylsulfonyl hydrazones has been developed. The generation of α- or β-substituted vinyl sulfones was affected by the

Full text of DOI:10.1016/j.tetlet.2016.07.099

Accepted Manuscript
PhI(OAc)2-mediated decomposition of N-arylsulfonyl hydrazones: Metal-free
synthesis of (E)-vinyl sulfones
Zaigang Luo, Yuyu Fang, Yu Zhao, Xuemei Xu, Chengtao Feng, Zhong Li,
Xiaomei Zhang, Jie He
PII:
S0040-4039(16)30967-4
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.07.099
TETL 47961
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
23 May 2016
19 July 2016
30 July 2016
Please cite this article as: Luo, Z., Fang, Y., Zhao, Y., Xu, X., Feng, C., Li, Z., Zhang, X., He, J., PhI(OAc)2-mediated
decomposition of N-arylsulfonyl hydrazones: Metal-free synthesis of (E)-vinyl sulfones, Tetrahedron Letters
(2016), doi: http://dx.doi.org/10.1016/j.tetlet.2016.07.099
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PhI(OAc)2-mediated decomposition of N-
arylsulfonyl hydrazones: Metal-free
synthesis of (E)-vinyl sulfones
Leave this area blank for abstract info.
Zaigang Luo,* Yuyu Fang, Yu Zhao, Xuemei Xu, Chengtao Feng, Zhong Li, Xiaomei Zhang and Jie He*
H
N
SO2Ar
α
SO2Ar
R1
R2
SO2Ar
R2
H
PhI(OAc)2, K2CO3
N
β
or
DMF, 80°C, 4h
R1
R1
Metal-fr ee
R2 = H
R2 = Me, Ph
R1 = aryl, Me
Environment-friendly
Regioselectivity
R2 = H, Me, Et, Ph
20 examples, up to 89% yield

1
Tetrahedron Letters
journal homepage: www.els evier.com
PhI(OAc)2-mediated decomposition of N-arylsulfonyl hydrazones: Metal-free
synthesis of (E)-vinyl sulfones
Zaigang Luo∗, Yuyu Fang, Yu Zhao, Xuemei Xu, Chengtao Feng, Zhong Li, Xiaomei Zhang and Jie He∗
College of Chemical Engineering, AnHui University of Science and Technology, Huainan, Anhui 232001, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
A novel and efficient approach for the preparing of (E)-vinyl sulfones via PhI(OAc)2-mediated
decomposition of ketone-derived N-arylsulfonyl hydrazones has been developed. The generation of
α- or β-substituted vinyl sulfones was affected by the steric hindrance at β-position of the
substrates. This transformation provides an environment-friendly and important complementary
strategy for the synthesis of various (E)-vinyl sulfones.
Received in revised form
Accepted
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Synthesis
Decomposition
N-arylsulfonyl hydrazones
(E)-vinyl sulfones
PhI(OAc)2
As we know, N-tosylhydrazones, derived from the
corresponding aldehydes or ketones, which were easily
In the past years, vinyl sulfones have gained increasing attention
for their important role in serving as key structural units of many
biological active compounds1 (e.g., as potent inhibitors of
cysteine protease1a and HIV-1 integrase1c ). Moreover, in the area
of synthetic organic chemistry, vinyl sulfones can act as versatile
building blocks for different kinds of organic transformations.2
Over the past several decades, many conventional synthetic
routes to the vinyl sulfone skeleton are well-documented.3
However, most of these procedures are very limited, such as
inaccessible starting materials, relatively harsh reaction
conditions, or generation of large amounts of unwanted
byproducts. Hence, the development of efficient methods for the
preparation vinyl sulfones is desirable.
decomposed under base or metallic salt conditions, have been
extensively utilized as the precursors of diazo compounds or
carbenes in recent years.9 Hence, the transition-metal-catalyzed
or metal-free decomposition of tosylhydrazones provides an
attractive alternative to the reported methods for the synthesis of
vinyl sulfones.
Prabhu's work
H
N
Ts
N
CNBr / TBAB
Ts
(a)
Ar
Ar
R
Ar
R
Wang's work
H
N
Recently, the direct cross-coupling of the sulfonyl derivative,
such as sodium sulfinate, sulfonyl hydrazide, sulfinic acid, thiols,
DMSO and so on, with an alkene,4 alkyne,5 terminal epoxide6 or
oxime acetate7 source for the synthesis of vinyl sulfones have
been well developed. The decarboxylative cross-coupling
sulfonylation of α,β-unsaturated carboxylic acids8 with sulfonyl
derivatives also have been an important research topic, for which
provided straightforward and efficient pathways to the formation
of carbon−sulfur bond under relatively mild conditions. Although
some methodologies are perfect for the synthesis of vinyl
sulfones, the discovery of diverse, readily available substrates or
sulfone sources is still highly demanded.
Ts
N
Cu(OAc)2 H2O
Ts
(b)
Ar
R
R
This work
H
N
SO2Ar
R2
SO2Ar
R2
N
PhI(OAc)2
SO2Ar
or
R1
(c)
R1
R1
Scheme 1 Synthesis of vinyl sulfones.
In 2015, Prabhu and co-workers revealed a novel reaction of
N-tosylhydrazone with CNBr and tetrabutylammonium bromide
∗ Corresponding author. Tel.: +86-554-666-8485; fax: +86-554-666-8485; e-mail: luozi139@163.com
∗ Corresponding author. Tel.: +86-554-666-8497; fax: +86-554-666-8497; e-mail: aust_jhe@163.com

2
Tetrahedron
(TBAB) for preparing vinyl sufones through a radical pathway,
Prabhu’ research,10 the substrate 1bg only afforded in suit or α-
substituted vinyl sulfone in CNBr–TBAB catalytic system.
Furthermore, when R1 was pyridyl or furyl group, (E)-vinyl
sulfone 2ah could not be isolated, while 2bh was isolated in 68%
yield. Very interestingly, the byproducts 2ah’ and 2bh’, which in
suit formed C-S bond generating α-substituted sulfone
compound, were also isolated and confirmed by NMR analysis
(Supporting Information).
in which the migration of a tosyl group was involved and has
been confirmed for the first time (Scheme 1a).10 Very recently,
the first CuII-catalyzed radical reaction to synthesis different
kinds of vinyl sulfones from readily available N-tosylhydrazones
was reported by Wang and co-workers (Scheme 1b).11 However,
both of them are still insufficient from an environment-friendly
point of view for the use of toxic nonmetal or metal catalyst. In
light of the nature of N-tosylhydrazones and previous work
above,10,11 we postulated that an oxidant cooperating with a base
might be used as a promising alternative to the CNBr/TBAB or
copper(II) catalytic system in the decomposition of N-
tosylhydrazones for the synthesis of vinyl sulfones. Herein, we
present an environmentally and efficient access to construct C-S
bond by means of N-S bond cleavage, via PhI(OAc)2-meditated
decomposition of N-arylsulfonyl hydrazones, affording (E)-vinyl
sulfones (Scheme 1c).
Table 1 Optimization of the reaction conditions a
H
Ts
N
Ts
N
Oxidant, Base
Solvent, Temp., 4h
2aa
1a
Entry
1
Oxidant
_
Base
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
_
Solvent
T(
80
)
Yieldb（%)
Accordingly, N-tosylhydrazone 1a was chosen as the model
substrate to seek optimal reaction conditions, including oxidant,
base, solvent, and temperature under ambient air. As depicted in
Table 1, when the reaction was carried out in the absence of any
oxidants or in the presence of H2O2 and K2S2O8 at 80 °C in 2 mL
of DMF using K2CO3 as the base, the corresponding product 2aa
was not obtained (Table 1, entries 1–3). Interestingly, treatment
1a in the presence of other oxidants, such as TBHP and BPO,
afforded the expected vinyl sulfones 2aa in 26% and 58% yield,
respectively (Table 1, entries 4–5). To our delight, the reaction
promoted by PhI(OAc)2 was proceeded well to furnish the
corresponding product 2aa in 86% yield (Table 1, entry 6).
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
DMA
CH3CN
n.d.
n.d.
n.d.
26
2
K2S2O8
H2O2
TBHP
BPO
80
80
80
80
80
80
80
80
80
80
80
3
4
5
58
6
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
86
7
35
Moreover, the product 2aa possessed complete
E
stereoselectivity (1H NMR analysis). When the reaction was
carried out with no base, a significant decrease of the yield was
observed (Table 1, entry 7). Changing the carbonate species, such
as Na2CO3 and Cs2CO3, led to inferior results (Table 1, entries 8–
9). Afterword, different solvents were evaluated. The identical
reaction performed in DMSO and DMA lowered the yield of the
product 2aa to 51% and 65%, respectively (Table 1, entries 10–
11). While no target compound 2aa was detected when CH3CN
was used as the solvent (Table 1, entry 12). Raising or decreasing
the loading of K2CO3 and PhI(OAc)2 did not deliver an
improvement in yield of product 2aa (Table 1, entry 13). Finally,
a diminished chemical yield was observed when the reaction
temperature was dropped to 70 °C or elevated to 90 °C (Table 1,
entries 14–15), which indicated that the reaction temperature
seemed to exert an important effect on the reactivity. Therefore,
the optimal reaction conditions were selected as shown in entry
6.
8
Na2CO3
Cs2CO3
K2CO3
K2CO3
K2CO3
32
9
68
10
11
12
51
65
n.d.
75c,63d
82e,39f
13
PhI(OAc)2
K2CO3
DMF
80
14
15
PhI(OAc)2
PhI(OAc)2
K2CO3
K2CO3
DMF
DMF
70
90
52
66
a Reaction conditions: 1a (0.2 mmol), oxidant (0.22 mmol), base (0.2 mmol),
d
solvent (2 mL), 4 h. Isolated yield. K2CO3 (0.3 mmol). K2CO3 (0.1
b
c
e
f
mmol). PhI(OAc)2 (0.33 mmol). PhI(OAc)2 (0.11 mmol). (DMF = N,N-
Dimethylformamide, DMSO Dimethylsulfoxide, DMA N,N-
With the established optimal conditions, the substrate scope
of this PhI(OAc)2-meditated decomposition reaction was
examined (Table 2). Firstly, when Ar was p-methylphenyl group,
and R1 was a phenyl ring with electron-withdrawing substituents
(p-NO2, p-CF3) or electron-donating substituents (p-Me), all of
the substrates 1ab-d gave the desired products with excellent E
stereoselectivity in good yields (2ab–d), showing no obvious
electronic effect in this transformation. The para- and meta-
substituted halogen atoms such as fluorine, bromine and chlorine
were well tolerated, affording the corresponding products in
moderate yields (2ae–g). Similarly, when Ar was phenyl group,
the substrates 1ba–f bearing different kinds of functional groups
on the phenyl ring of R1, such as methyl, methoxyl, nitro and
chloro groups, all reacted smoothly to afford the desired (E)-
vinyl sulfones in good yields (2ba–2bf). Notably, when R1 was
naphthenyl group, sulfonyl hydrazone 1bg is also a suitable
substrate for this reaction giving the expected product 2bg in
good yields (75%) as well as Wang’ report.11 According to the
=
=
Dimethylacetamide, TBHP = tert-butyl hydroperoxide (70% in aqueous),
BPO = Benzoylperoxide, n.d. = not detected.
Afterwords, the reaction efficiency affected by steric effects
was also considered. Gratifyingly, under the standard conditions,
N-arylsulfonyl hydrazones 1ai and 1bi bearing a phenyl group at β-
position could be smoothly transformed into vinyl sulfones 2ai
and 2bi in 68% and 70% yields, respectively (Scheme 2).
However, the C–S bond formed at α- or β-position of the
substrates is difficult to distinguish because of the same
substituted phenyl groups. In order to make clear at which
position tosyl or benzenesulfonyl group will react under
PhI(OAc)2-mediated conditions, N-tosylsulfonyl hydrazone 1aj
bearing a ethyl group at β-position and N-benzenesulfonyl
hydrazone 1bj bearing a methyl group at β-position were selected
as the reaction substrates (Scheme 2). To our surprise, the C–S

3
bond was formed at α-position generating products 2aj and 2bj
under standard conditions, whose structures can be easily identified
by 1H NMR analysis (Supporting Information). The reports on the
α-substituted vinyl sulfones generated from decomposition of N-
sulfonyl hydrazones are rare and unprecedented.10 Accordingly,
the tosyl group of 2ai and the benzenesulfonyl group of 2bi
should locate at the same position, namely α-position. The steric
hindrance at β-position of the substrates seemed to exert an
important effect on the reaction regioselectivity under our
standard conditions, which are different from the Prabhu’s and
Wang’s research results. Under copper-catalyzed condition
(Wang’ work),11 the tosyl group exclusively reacted at β-position
of the substrates producing (E)-vinyl sulfones. And under
Prabhu’s reaction conditions (CNBr–TBAB),10 the tosyl group
underwent 1,2-sulfone migration procedure and the C–S bond
was constructed at β-position of the N-tosylhydrazone substrates.
The observed results might provide the possibility for further
functionalization of α-substituted vinyl sulfones.
of cyclopentanone with PhI(OAc)2 formed mainly the sulfone
byproduct 2bl’ in good yield (79%) (Scheme 3). Further
investigation focused on expanding the scope of substrates of this
method is currently in progress.
H
N
SO2Ar
SO2Ar
N
standard conditions
β
β
α
α
Ph
Ph
2ai, 68%
2bi
1ai Ar = p-MeC6H4
, 70%
1bi
Ar = Ph
H
N
SO2Ar
SO2Ar
N
standard conditions
β
α
β
α
R2
R2
2aj, 66%
2bj
1aj Ar = p-MeC6H4, R2 = Et
1bj
, 70%
Ar = Ph, R2 = Me
Table 2 Synthesis of various (E)-vinyl sulfones a
Scheme 2 Synthesis of α-substituted vinyl sulfones.
H
N
SO2Ar
SO2Ar
PhI(OAc)2 (1.1 equiv)
K2CO3 (1.0 equiv)
N
O
PhO2S NH HN SO2Ph
Ph
R1
R1
DMF, 80°C, 4h
standard conditions
S
N2
N
N
1a
Ar = p-MeC6H4
1b Ar = Ph
O
2
2bk, 89%
1bk
Ts
Ts
Ph
Ph
S
Ts
NNHSO2Ph
O
S
O
O
O
standard conditions
O2N
Me
2ac, 79%
1bl
2ab, 82%
2aa, 86%
2bl
, trace
2bl', 79%
Ts
Ts
Ts
Scheme 3 Synthesis of aliphtic vinyl sulfones.
Br
F3C
F
2af, 77%
2ad, 85%
2ae, 69%
H
N
Ts
Ts
N
Ts
standard conditions
Ts
Ts
Cl
TEMPO (2 equiv)
N
N
2aa, 0%
1aa
2ah', 76%
2ah, trace
2ag, 72%
SO2Ph
SO2Ph
Scheme 4 Control experiment.
SO2Ph
Me
2bb
MeO
Ph
N
OAc
Ph
OAc
R2
Ph
N
OAc
I
I
I
H
N
2bc
, 89%
SO2Ar
R2
, 82%
2ba, 82%
PhI(OAc)2
HOAc
N
N
N
N
SO2Ar
R2
N
R2
SO2Ph
R1
SO2Ph
SO2Ph
R1
R1
R1
ArSO2
1
B
A
B'
Cl
N2
O2N
NO2
2bf
, 73%
OAc
2be
Ph
R1
2bd
, 71%
, 77%
Ph
R1
OAc
I
I
ArSO2
R2 = H
SO2Ar
base
R2
SO2Ph
SO2Ar
SO2Ph
R1
β−
SO2Ph
C
2
PhI
HOAc
D'
substituted
ArSO2
R2 = CH3, Ph
O
O
OAc
R2
Ph
2bh', 20%
2bg, 75%
2bh, 68%
SO2Ar
I
base
a
Reaction conditions: 1 (0.2 mmol), PhI(OAc)2 (0.22 mmol), K2CO3 (0.2
R1
R1
R2
2
substituted
mmol), DMF (2 ml). Isolated yield.
PhI
HOAc
SO2Ar
−
a
D
Interestingly, this strategy is also compatible with N-
benzenesulfonyl hydrazone 1bk of aliphatic ketone, such as
acetylacetone, which in reaction with PhI(OAc)2 furnished the
corresponding aliphatic α-substituted vinyl sulfone 2bk in
excellent yield (89%) (Scheme 3). However, the hydrazone 1bl
Scheme 5 Plausible reaction mechanism.

4
Tetrahedron
To gain an insight into the reaction mechanism, 2.0 equiv.
806. (c) Popoff, I. C.; Denver, J. L. J. Org. Chem. 1969, 34, 1128;
(d) Gancarz, R. A.; Kice, J. L.; Tetrahedron Lett. 1980, 21, 4155;
(e) Hopkins, P. B.; Fuchs, P. L. J. Org. Chem. 1978, 43, 1208; (f)
Kirihara, M.; Yamamoto, J.; Noguchi, T.; Hirai, Y. Tetrahedron
Lett. 2009, 50, 1180; (g) Huang, X.; Duan, D. H.; Zheng, W. X. J.
Org. Chem. 2003, 68, 1958.
radical scavenger reagent, 2,2,6,6-tetramethyl-1-piperidinyloxy
(TEMPO), was introduced into the standard reaction system
(Scheme 4). Obviously, the reaction was inhibited and no product
2aa was obtained, which indicated that a free radical process
might be involved of this transformation.
4. (a) Zhang, N.; Yang, D.; Wei, W.; Yuan, L.; Cao, Y.; Wang, H.
RSC Adv. 2015, 5, 37013; (b) Meyer, A. U.; Jäger, S.; Hari, D. P. ;
Künig, B. Adv. Synth. Catal. 2015, 357, 2050; (c) Tang, S.; Wu,
Y.; Liao, W.; Bai, R.; Liu, C.; Lei, A. Chem. Commun. 2014, 50,
4496; (d) Li, X.; Xu, Y.; Wu, W.; Jiang, C.; Qi, C.; Jiang, H.
Chem. Eur. J. 2014, 20, 7911; (e) Gao, X.; Pan, X.; Gao, J.;
Huang, H.; Yuan, G.; Li, Y. Chem. Commun. 2015, 51, 210; (f)
Fan, W.; Su, J.; Shi, D.; Feng, B. Tetrahedron 2015, 71, 6740; (g)
Sawangphon, T.; Katrun, P.; Chaisiwamongkhol, K.; Pohmakotr,
M.; Reutrakul, V.; Jaipetch, T.; Soorukram, D.; Kuhakarn, C.
Synth. Commun. 2013, 43, 1692.
On the basis of the results above and previous related
literature,10,11 a plausible mechanism is proposed (Scheme 5).
Initially, intermediate A was formed in the presence of
PhI(OAc)2, which might generate arylsulfonyl radical and
nitrogen-centered radical B resonating with carbon-centered
radical B’ by means of N-S bond cleavage. Subsequently, radical
C could be readily accessed with the release of molecular
nitrogen from radical B’. Next, the recombination of arylsulfonyl
radical produced from previous steps with radical C would
generate intermediate D for the steric hindrance, or intermediate
D’ when R2 was hydrogen atom. Eventually, α- or β-substituted
vinyl sulfones 2 were obtained via reductive elimination of
complex D or D’ under base conditions. Studies of the more
detailed mechanism of this process are ongoing.
5. (a) Xu, Y.; Zhao, J.; Tang, X.; Wu, W.; Jiang, H. Adv. Synth.
Catal. 2014, 356, 2029; (b) Taniguchi, N. Tetrahedron 2014, 70,
1984; (c) Li, X.; Shi, X.; Fang M.; Xu, X. J. Org. Chem. 2013, 78,
9499; (d) Li, X.; Xu, X.; Shi, X. Tetrahedron Lett. 2013, 54, 3071;
(f) Rong, G.; Mao, J.; Yan, H.; Zheng Y.; Zhang, G. J. Org.
Chem. 2015, 80, 4697; (g) Li, S.; Li, X.; Yang F.; Wu, Y. Org.
Chem. Front. 2015, 2, 1076; (h) Xi, Y.; Dong, B.; McClain, E. J.;
Wang, Q.; Gregg, T. L.; Akhmedov, N. G.; Petersen, J. L.; Shi, X.
Angew. Chem. Int. Ed. 2014, 53, 4657; (i) Wei, W.; Li, J.; Yang,
D.; Wen, J.; Jiao, Y.; You, J.; Wang, H. Org. Biomol. Chem. 2014,
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In summary, we have developed a novel and practical method
for the synthesis of (E)-vinyl sulfones via PhI(OAc)2-mediated
decomposition of N-arylsulfonyl hydrazones. The reaction
regioselectivity was affected by the steric hindrance at β-position
of the substrates, namely α- or β-substituted vinyl sulfones were
generated depending on whether the β-position of the substrates
with a substituted group or not. Preliminary mechanistic study
indicated that the reaction procedure might undergo a radical
pathway. It is noted that this transformation futures metal-free,
nontoxic mediator, mild condition, broad substrate scope,
excellent E stereoselectivity and high yield, which represents an
environmentally and efficient access to the C–S bond
construction.
6. Chawla, R.; Kapoor, R.; Singh A. K.; Yadav, L. D. S. Green
Chem. 2012, 14, 1308.
7. Tang, X.; Huang, L.; Xu, Y.; Yang, J.; Wu W.; Jiang, H. Angew.
Chem. Int. Ed. 2014, 53, 4205.
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Rokade, B. V. and Prabhu, K. R. J. Org. Chem. 2014, 79, 8110;
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Acknowledgments
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (21102003)
and National Natural Science Foundation of Anhui Province
(1608085MB38).
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5
PhI(OAc)2-mediated decomposition of N-
arylsulfonyl hydrazones: Metal-free
synthesis of (E)-vinyl sulfones
Zaigang Luo,* Yuyu Fang, Yu Zhao, Xuemei Xu, Chengtao
Feng, Zhong Li, Xiaomei Zhang and Jie He*
Highlights:
(1) Metal-free synthesis of (E)-vinyl sulfones
(2) Using nontoxic environment-friendly PhI(OAc)2
as mediator
(3) Regioselectivity (generation of α- or β-
substituted vinyl sulfones)
(4) Broad substrate scope (aromatic and aliphatic
ketone-derived hydrazones)