Simultaneous Construction of C?Se And C?S Bonds via the Visible-Light-Mediated Multicomponent Cascade Reaction of Diselenides, Alkynes, and SO2

Article abstract of DOI:10.1002/asia.201901049

A visible-light mediated multicomponent cascade reaction of diselenides, alkynes, and sulfur dioxide was developed, in which multiple C?Se and C?S bonds were constructed, and unexpected β-sulfonylvinylselane compounds were generated with high selectivity for E configuration. β-Sulfonylvinylselane transformation into 1,4-oxathiine-4,4-dioxide and sulfonylethyne derivates was then investigated. A plausible mechanism involving a selenium radical-initiated cascade reaction and sulfur dioxide insertion was proposed.

Full text of DOI:10.1002/asia.201901049

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Simultaneous construction of C-Se and C-S bonds via the visible-
light mediated multicomponent cascade reaction of diselenides,
alkynes and SO2
Authors: Yanyan Chen, Hui Chen, Rui Ding, Haitao Tang, Yingming
Pan, and Yanli Xu
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To be cited as: Chem. Asian J. 10.1002/asia.201901049
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Chemistry - An Asian Journal
10.1002/asia.201901049
COMMUNICATION
Simultaneous construction of C–Se and C–S bonds via the
visible-light mediated multicomponent cascade reaction of
diselenides, alkynes, and SO
2
[a]
[b]
[b]
[b]
[a]
[a]
Hui Chen, Rui Ding, Haitao Tang, Yingming Pan, Yanli Xu* , and Yanyan Chen*
Dedication ((optional))
Abstract: A visible-light mediated multicomponent cascade reaction
of diselenides, alkynes, and sulfur dioxide was developed, multiple
C–Se and C–S bonds were constructed, and unexpected β-
sulfonylvinylselane compounds in high selectivity for E configuration
were generated. β-Sulfonylvinylselane transformation into 1,4-
oxathiine 4,4-dioxide and sulfonylethyne derivates was then
investigated. A plausible mechanism involving selenium radical-
initiated cascade reaction and sulfur dioxide insertion was proposed.
[
1]
Given their wide application in pharmacology, the synthesis of
selenium-containing compounds has attracted great interest. As
a class of stable and available source of selenium, diselenides
are preferred as selenylating agents. Selenium has been
[
2]
[3]
[4]
[5]
introduced into benzofuran, indole, naphthalene, benzene,
[
6]
and unsaturated alkenes by using diselenides as the source
via the electrophilic seleniranium cation pathway. A selenium
moiety can also be introduced via radical addition reaction. Sun
and
selenodifluoromethylation of alkenes promoted by copper salt.
Ogawa’s group developed multicomponent cascade reactions of
co-workers
reported
a
radical-initiated
[
7]
[
8]
[9]
diselenide, alkyne with alkene,
benzoyl peroxide,
and
[10]
(
2 2
Ph P)
(Scheme 1a). The multicomponent cascede reactions
induced by selenium radical are effective in synthesizing
organoselenium compounds. However, related reports are
limited.
Scheme 1. Multicomponent cascade reaction initiated by selenium radical and
two strategies for sulfur dioxide insertion.
Sulfur dioxide insertion is an attractive route for the sulfonyl
The second strategy involves the radical being attacked by other
functional groups, then another radical intermediate is generated
2 2
compound synthesis. DABCO•(SO ) and inorganic sulfites are
widely used as a substitute for sulfur dioxide due to their
convenient operation. Two strategies are applied into sulfur
[
13]
and will be captured by sulfur dioxide.
The intramolecular
[
11]
cyclization of in situ generated radicals are commonly used in
the second strategy, thereby produce limited substrates. Visible
light photocatalysis can activate various substrates into radical
intermediates and has attracted growing interest during the past
dioxide insertion via the radical pathway (Scheme 1b).
The
first strategy involves the radical being trapped by sulfur dioxide,
producing a sulfonyl radical that reacts with other substrates and
[
12]
generates sulfonyl compounds.
Unavailable substrates, such
[
14]
years,
been recently explored.
We previously explored the visible-light induced cyclization of
and the photoinduced insertion of sulfur dioxide has
as aryl diazonium salts, periodate, hydrazides, and potassium
alkyltrifluoroborates, are commonly applied in this strategy.
[
15]
[16]
1
,6-enynes with diselenides.
We speculated that the
[
[
a] H. Chen, Dr. Y. Xu and Dr. Y. Chen
Pharmacy School
selenium-substituted vinyl radical can be trapped by sulfur
dioxide and undergo subsequent reaction. Herein, we report a
visible-light mediated multicomponent cascade reaction of
diselenides, alkynes, and sulfur dioxide. Through this cascade
reaction, novel β-sulfonylvinylselanes were prepared via the
second strategy. Furthermore, the transformations of the
obtained β-sulfonylvinylselanes into 1,4-oxathiine 4,4-dioxide
and sulfonylethyne derivates are explored.
Guilin Medical University
541004 People’s Republic of China
E-mail: chenyy269614@163.com
b] D. Rui, Dr. H. Tang and Prof. Y. Pan
State Key Laboratory for the Chemistry and Molecular Engineering of
Medicinal Resources
Guangxi Normal University
Initially, the reaction of phenylacetylene 1a, 1,2-
541004 People’s Republic of China
2 2
diphenyldiselane 2a and DABCO•(SO ) was performed in the
Supporting information for this article is given via a link at the end of the
document
catalysis of 5 mol% acridinium salt under the irradiation of 12 W
blue LEDs. An unexpected product 3a in 29% yield was obtained
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COMMUNICATION
[
a]
Table 1. Optimization of the reaction conditions.
[a]
Scheme 2. Substrate Scope.
[
b]
Entry
Photocatalyst
Mes-Acr-Ph BF
Solvent
Yield (%)
29
36
63
64
71
43
34
10
trace
0
26%
60
+
1
2
3
4
5
6
7
8
9
4
CH
CH
CH
CH
CH
3
3
3
3
3
CN
CN
CN
CN
CN
Ru(bpy)
Ir(bpy)(ppy)
Na -Eosin Y
3
Cl
2
2
PF
6
2
-
-
-
-
-
-
-
-
DCE
1,4-dioxane
DMSO
MeOH
toluene
1
0 [
c]
1
1
CH
CH
3
CN
CN
[
d]
e]
f]
12
13
14
15
16
3
[
[
[
[
-
-
-
-
CH
CH
CH
CH
3
3
3
3
CN
CN
CN
CN
66%
trace
46%
0
g]
h]
[
a]
Reaction conditions: 1a (0.4 mmol), 2a (0.3 mmol), photocatalyst (5
mol %) and DABCO•(SO (0.3 mmol) in solvent (3 mL) was stirred at air
atmosphere under the irradiation of 12 W blue LEDs for 6 h at rt.
2 2
)
[
b]
Isolate
[
c]
[d]
yields.
DABCO•(SO
2
)
2
was replaced by
K
2
S
O
2 5
(0.3 mmol).
[
e]
[f]
DABCO•(SO
)
2 2
(0.4 mmol) was used.
Argon atmosphere.
Oxygen
[
g]
[h]
atmosphere. 12 W white LEDs was used. The reaction was conducted in
the dark.
(
entry 1, Table 1). Further conditions were examined, and the
results are shown in Table 1. Photocatalysts, such as
Ru(bpy) Cl Ir(bpy)(ppy) PF and Na -Eosin Y, were
3
2
,
2
6
,
2
investigated and produced 3a in 36%–64% yields (entries 2–4,
Table 1). When the photocatalyst was removed, 3a was obtained
in an increased yield of 71% (entry 5, Table 1). Other solvents,
such as DCE, 1,4-dioxane, DMSO, MeOH, and toluene, were
explored and found to be unsuitable for this reaction because of
the decreased product yield (entries 6–10, Table 1).
[
a]
Reaction conditions: 1 (0.4 mmol), 2 (0.3 mmol) and DABCO•(SO
mmol) in CH CN (3 mL) was stirred at air atmosphere under the irradiation of
2 W blue LEDs for 6 h at rt. Na
reaction was performed for 3 h.
2 2
) (0.3
DABCO•(SO
6% yield (entry 11, Table 1). The amount of DABCO•(SO
increased to 2.0 equiv., and 3a was obtained in 60% yield (entry
2, Table 1). Argon and oxygen atmospheres were also
2 2 2 2
) was replaced by K S O5, generating 3a of only
3
[
b]
[c]
1
2
-Eosin Y was added (5 mol % ). The
2
2 2
)
was
1
investigated, 3a was obtained in 66% yield in argon atmosphere,
whereas only trace amount of 3a was observed in oxygen
observed. When 3-ethynylpyridine was used, the reaction was
smooth and generated 3m in 42% yield. Meanwhile, the isomer
[
17]
atmosphere (entries 13 and 14, Table 1).
was applied, and 3a in 46% yield was obtained (entry 15, Table
). When the reaction was conducted in the dark, no product
was observed (entry 16, Table 1). Finally, 1.5 equiv. of
DABCO•(SO was applied, and the use of CH CN as solvent
The white LEDs
3
m′was obtained in 3% yield, and its structure was also
[
18]
determined by single-crystal X-ray diffraction analysis. In the
diselenide moiety, 4-Me, 4-CF3, and 4-Cl groups generated the
corresponding products 4a–4c in 61%–64% yields. When 1,2-
di(thiophen-3-yl)diselane was used as substrate, only trace
amount of 4d was observed, and almost the all phenylacetylene
was transferred into ((1-phenylethene-1,2-diyl)bis(selanediyl))-
dithiophene. Alkyl diselenides were also investigated. 1,2-
Dibenzyl-diselane generated 4e in 59% yield. The cascade
reactions of 1,2-dimethyldiselane with phenylacetylene, 4-
1
2
)
2
3
under the irradiation of blue LEDs for 6 h were the best
conditions.
With the best conditions in hand, the substrate scope of
alkynes and diselenides was investigated, and the results were
summarized in Scheme 2. Various substitutes such as halogen,
methyl, methoxy, nitro, methoxycarbonyl and amino were
suitable and reacted smoothly. Thus, 3b–3j were generated in
moderate yields from 35% to 71%. When 4-ethynyl-1,1'-biphenyl
was introduced, 3k was produced in 54% yield, and its structure
bromophenylacetylene,
4-methylphenylacetylene
and
3-
ethynylthiophene produced 4f–4i in 47%–64% yields. When the
disulfide was applied, only trace amount of 4j was produced.
[
18]
was determined by single-crystal X-ray diffraction analysis.
Alkyl acetylene was unsuitable for this reaction, and no 3l was
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COMMUNICATION
Scheme 5. Possible mechanism.
[20]
63% yield with a Z/E ratio of 1:7 (eqn [2], Scheme 4).
The
addition of 1,1-diphenylethylene reduced 3a yield to 42%, and
no coupling product of 1,1-diphenylethylene was detected (eqn
[
3], Scheme 4). On the basis of control experiments and
[
8], [16]
reported literatures,
a possible mechanism was proposed
(
Scheme 5). Firstly, the diselenide was excited into selenium
radical under blue light irradiation. The addition with 1a provided
a preferred vinylic radical intermediate A, which was then
captured by sulfur dioxide. A sulfonyl radical intermediate C was
generated. The following attack to 1a produced the vinylic
radical intermediate D, which was trapped by diselenide. Finally,
product 3a was generated, and selenium radical was provided
Scheme 3. Transformation of the obtained β-sulfonylvinylselanes.
We further investigated the transformations of the obtained β-
[19]
sulfonylvinylselanes (Scheme 3). Firstly, 3a was oxidized into
selenoxide under the addition of 3-chloroperoxybenzoic acid,
which was then promoted by KOH and generated 1,4-oxathiine
[
8c]
for recycling.
In conclusion, we developed
multicomponent cascade reaction of diselenides, alkynes, and
sulfur dioxide, and prepared novel class of β-
sulfonylvinylselanes in high selectivity for configuration.
Furthermore, the transformations of the obtained β-
a
visible-light mediated
4,4-dioxide 5a in 70% yield. When water was replaced by
ammonia water, 5b was obtained in 56% yield. The ethylene
glycol was also introduced, the expected 5c wasn’t observed,
but an unexpected 5d was obtained in 64%. Ethanolamine was
not suitable, and no major product was obtained.
a
E
sulfonylvinylselanes
into
1,4-oxathiine4,4-dioxide
and
To explore the mechanism, we performed several control
experiments (Scheme 4). A crossing experiment of 1e and 1g
was conducted in the standard conditions, generating 3e and
sulfonylethyne derivates were investigated.
A
possible
mechanism involving selenium radical-initiated multicomponent
cascade reaction promoted by visible light was also proposed.
3ge in 20% and 33% yields, respectively (eqn [1], Scheme 4).
When 1.5 equiv. of Tempo was added in the standard reaction,
only trace amount of 3a was produced, and 6a was obtained in
Acknowledgements
We thank the National Natural Science Foundation of China
(
21861006 and 21861015), Natural Science Foundation of
Guangxi (2018GXNSFBA138050 and 2017GXNSFBA198205),
Special Fund for Talents of Guangxi (AD18281028 and
AD18281035).
Keywords: visible-light initiation; multicomponent cascade
reaction; sulfur dioxide insertion;
β-sulfonylvinylselane
compounds; product’s transformation
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[
Only trace amount of 3a was observed, side product such as 2-oxo-2-
phenylacetaldehyde was detected by GC-MS.
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a
b
b
Hui Chen, Rui Ding, Haitao Tang,
b
a
Yingming Pan, Yanli Xu* and Yanyan
a
Chen*
Page No. – Page No.
Simultaneous construction of C-Se
and C-S bonds via the visible-light
mediated multicomponent cascade
reaction of diselenides, alkynes and
Text for Table of Contents
SO
2
2
A visible-light induced cascade reaction of diselenides, alkynes and SO and afforded novel
β-sulfonylvinylselanes as product. The transformation of the obtained product was also
investigated.
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