Catalyst-free visible-light-initiated oxidative coupling of aryldiazo sulfones with thiols leading to unsymmetrical sulfoxides in air

Article abstract of DOI:10.1039/c9gc00222g

A facile and efficient visible-light-driven method has been developed to construct sulfoxides via oxidative coupling of aryldiazo sulfones with thiols using the O₂ in air as the oxidant. This reaction could be performed at room temperature under catalyst- and additive-free conditions. The present methodology offers a mild and environmentally benign approach to obtain a library of sulfoxides in good yields with favorable functional group tolerance.

Full text of DOI:10.1039/c9gc00222g

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Catalyst-free visible-light-initiated oxidative coupling of aryldiazo
sulfones with thiols leading to unsymmetrical sulfoxides in air
Received 00th January 20xx,
Accepted 00th January 20xx
†
†
Qishun Liu,a Leilei Wang,a Huilan Yue,b Jiang-Sheng Li,c ZidanLuod and Wei Wei*a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
A facile and efficient visible-light-driven method has been
developed to construct sulfoxides via oxidative coupling of
aryldiazo sulfones with thiols using the O2 in air as the oxidant.
This reaction could be performed at room temperature under
catalyst- and additive-free conditions. The present methodology
offers a mild and environmentally benign approach to a library of
sulfoxides in good yields with favorable functional group tolerance.
Sulfoxides are highly valuable building blocks, which constitute the
key structural motifs of many natural products,1 biologically active
molecules2 and drug candidates.3 Representative marketed
therapeutics are Nexium4a and Provigil.4b Furthermore, sulfoxides
have also been widely employed in material,5 organocatalysis6 and
organometallic chemistry.7 As a consequence, the direct synthesis
of sulfoxides has gained significant attention in organic chemistry.
Generally, sulfoxides are synthesized by nucleophilic displacement
of sulfinyl derivatives with organometallic reagents8 and transition-
metal-catalyzed oxidation reactions of sulfides in the presence of
stoichiometric amount of hypervalent iodine reagents or
peroxides.9 Nevertheless, the use of metal reagents and hazardous
oxidants make these methods suffer from some drawbacks
including the generation of stoichiometric quantities of toxic wastes,
limited functional group tolerance or over-oxidation of sulfoxides to
sulfones. Although some progress has been made over the past
decade,10 the development of mild, facile, efficient, and selective
methods to access sulfoxides still remains in highly demand.
Scheme 1 Visible-light-induced methods for the synthesis of
sulfoxides from thiols.
metal photocatalysts has proved to be a safer alternative to
traditional methods.12 Nevertheless, this strategy usually
needs the extra steps to prepare sulfides from the
corresponding thiols. Recently, visible-light-induced tandem
reactions for the direct construction of sulfoxides from
commercially available thiols have been reported.13,14 For
example, Yadav, Alemάn and our group independently
described visible-light promoted sulfoxidation of alkenes with
thiols leading to β-keto sulfoxides or sulfoxides.13 In 2018, Lee
presented visible-light-driven AgNO3-catalyzed method to
construct diaryl sulfoxides and diaryl sulfones from diazonium
salts and arylthiols using K2S2O8 as the oxidant.14 However, the
limited substrate scope and utilization of metal catalyst would
limit their applications in synthetic chemistry.
In recent years, visible light as clean and renewable
chemical energy has been widely utilized to promote various
organic synthetic transformations.11 In this context, the
oxidation of sulfides using dioxygen catalyzed by different
a. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu
273165, Shandong, China
b. Qinghai Provincial Key Laboratory of Tibetan Medicine Research and Key
Laboratory of Tibetan Medicine Research, Northwest Institute of Plateau Biology,
Chinese Academy of Sciences, Qinghai 810008, China
c. School of Chemistry and food Engineering, Changsha University of Science and
Technology, Changsha, 410114, P. R. China
As our continued studies focusing on the photochemical
reactions15 and synthesis of sulfur-containing compounds,16
here, we wish to report a facile and efficient visible-light-
induced method for the selective construction of sulfoxides
from readily available aryldiazo sulfones and various thiols
using the O2 in air as the oxidant. This reaction could be
conducted under mild and photocatalyst-free conditions to
d School of Chemistry and Chemical Engineering, Hunan University of Science and
Technology, Xiangtan 411201, P. R. China
*E-mail: weiweiqfnu@163.com
†These authors contributed equally to this work.
‡ Electronic Supplementary Information (ESI) available: Experimental details. See
DOI: 10.1039/b000000x/
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give various sulfoxides in moderate to good yields with CH3CN/H2O (1/1) (entry 18). The yield was slightly reduced
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DOI: 10.1039/C9GC00222G
favorable functional group tolerance.
when the reaction was conducted under irradiation with 3 W
white or 3 W green LED lamps (entries 22 and 23). In addition,
no transformation was observed when the reaction was
carried out without light irradiation (entry 24).
Table 1 Optimization of reaction conditions.a
Table 2 Visible-light-induced direct aerobic oxidative synthesis
of sulfoxides from aryldiazo sulfones and thiols in air.a,b
Entry
Photocatalyst (mol %) Solvent
Yield(%)b
59
56
60
57
CH3CN/H2O (9/1)
1
Eosin Y (2)
Na2-eosin Y (2)
CH3CN/H2O (9/1)
CH3CN/H2O (9/1)
CH3CN/H2O (9/1)
CH3CN/H2O (9/1)
CH3CN/H2O (9/1)
CH3CN/H2O (9/1)
DME/H2O (9/1)
THF/H2O (9/1)
2
Eosin B (2)
3
Acridine Red (2)
4
Rhodamine B (2)
55
61
62
32
38
15
0
5
Rose Bengal (2)
6
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
7
8
9
DCE/H2O (9/1)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Toluene/H2O (9/1)
1,4-dioxane/H2O (9/1)
Acetone/H2O (9/1)
EtOH/H2O (9/1)
CH3CN/H2O (4/1)
CH3CN/H2O (3/1)
CH3CN/H2O (2/1)
CH3CN/H2O (1/1)
CH3CN/H2O (1/2)
CH3CN
20
30
38
66
69
72
79
43
30
0
H2O
49c
42d
0e
CH3CN/H2O (1/1)
CH3CN/H2O (1/1)
CH3CN/H2O (1/1)
a Reaction conditions: 1a (0.3 mmol), 2a (0.1 mmol), photocatalyst
b
(2 mol %), solvent (2 ml), 3 W blue LED lamps, rt, air, 16h.
Isolated yields based on 2a. c 3 W white LED lamps. d 3 W green
LED lamps. e Without visible-light irradiation.
The initial studies began with
a
reaction of 1-(4-
1a and
methoxyphenyl)-2-(methylsulfonyl)diazene
(
)
benzenethiol (2a) under irradiation of 3 W blue LED lamps
(Table 1). As shown in entry 1, when the model reaction was
conducted in CH3CN/H2O (v/v = 9/1) in the presence of Eosin Y
(2 mol %) at room temperature in air, the desired product 3aa
was isolated in 59% yield. Furthermore, the screening of
various photocatalysts found that the yield was not obviously
affected by changing of different catalyst (entries 2-6). To our
delight, a 62% yield of 3aa was obtained when the model
reaction was carried out in the absence of any photocatalyst
(entry 7). Next, efforts to improve the reaction efficiency then
shifted to investigate the solvent effect (entries 8-21). The
result showed that CH3CN/H2O (9/1) was superior to other
mixtures of organic solvent and water (entries 8-14). Further
optimization suggested that the yield was greatly improved by
increasing of the ratio of water (entries 8-21). The best yield
(79%) was obtained when the reaction was performed in
a Reaction conditions: 1 (0.3 mmol), 2 (0.1 mmol), CH3CN/H2O(1/1)
(2 mL), 3 W blue LED lamps, rt, air, 16 h. b Isolated yields based on
2.
c 40 h.
With the optimized reaction conditions in hand, the scope of
the aerobic oxidative synthesis of sulfoxides from aryldiazo
sulfones and thiols was examined. Generally, aryl thiols
containing electron-donating and electron-withdrawing groups
on the aryl rings were all easily converted to the corresponding
products (3aa-3aj) in good yields. The steric effect was also
evaluated under optimal reaction conditions. The reaction
2 | J. Name., 2012, 00, 1-3
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efficiency of sterically hindered substrates such as ortho-
methyl and methoxy substituted aryl thiols was not affected by
steric effect, and the desired products (3ac and 3ad) were
obtained in 80% and 82% yields, respectively. This
photocatalytic reaction also possessed good functional group
compatibility, and some functionalities such as chloro, bromo,
fluoro, methoxy and hydroxyl groups were also tolerated to
afford the corresponding products, which can be applied in
further transformations. In addition, when heterocycle
arylthiols such as 5-methyl-1,3,4-thiadiazole-2-thiol and
benzo[d]thiazole-2-thiol were employed in reactions, the
desired products 3ak and 3al were also obtained in moderate
yields. Notably, aliphatic thiols such as 2-phenylethanethiol,
View Article Online
DOI: 10.1039/C9GC00222G
phenylmethanethiol,
mercaptoacetate were also well compatible with this process,
affording the desired products in good yields (3am 3ap).
butane-1-thiol
and
methyl
2-
-
Moreover, the scope of this procedure was also expanded to a
series of arylazo sulfones, in addition to 1-(4-methoxyphenyl)-
2-(methylsulfonyl)diazene 1a
,
other arylazo sulfones
regardless of their electronic and steric effects were also well
applied in the reaction system to give the corresponding
products (3ba-3ia) in moderate to good yields.
To gather some mechanistic insights of this transformation,
several control experiments were carried out as shown in
Scheme 2. It is known aryl radicals are readily formed from
arylazo sulfones under visible light irradiation.17 Thus, the
present transformation might undergo through a radical
pathway. Initially, the model reaction was significantly
inhibited when TEMPO (well known radical-capturing species)
was added into reaction system, and aryl-TEMPO adduct was
detected LC-MS (Scheme 2, (1)). This result suggested that a
radical process should be involved in the present reaction.
Furthermore, when the model reaction was conducted under
N2, only a trace amount of the product was detected, which
indicated that O2 in air is necessary for this transformation
(Scheme 2, (2)). Subsequently, isotope labeling experiment
using H218O was performed in air to elucidate the source of
oxygen in sulfoxide, and the result showed that oxygen atom
of sulfoxide derived from O2 in air (Scheme 2, (3)). A singlet
oxygen (1O2) might be involved in this oxidation process.18 To
Scheme 2 Preliminary mechanistic studies
Based on the above experimental results and previous reports,17-
a plausible reaction mechanism was proposed as illustrated in
21
Scheme 3. Initially, the 1nπ* state of the arylazosulfone 1 was
generated under the visible-light irradiation.17 Then, aryl radical A
was formed through the homolysis of N-S bond occurring from the
1nπ* state along with the subsequent release of N2.17 On the other
hand, the oxidation of thiol 2 by O2 in air would produce thiyl
radical B,20 which underwent a homocoupling process to afford
disulfide 4. Subsequently, the coupling of aryl radical A with
disulfide 4 would lead to the formation of the sulfide 5 and
regeneration of thiyl radical B. Finally, the oxidation of sulfide
intermediate 5 by 1O2 produced the desired sulfoxide 3.21
1
test this hypothesis, DABCO, a well known strong O2 physical
quencher,19 was added to the model reaction. As expected,
none of the desired product was detected, which indicated
1
that this transformation should involve O2-mediated process
(Scheme 2, (4)). Next, when the reaction of 4-
methoxyphenylazo mesylate (1a) and 1,2-diphenyldisulfide (4a
was carried out under standard conditions, the desired
product 3aa was obtained in 68% yield, indicating that the
disulfide might be involved in this reaction system (Scheme 2,
)
(5)). Moreover, in addition to product 3aa, sulfide 5a was also
isolated in 45% yield when the model reaction was conducted
for 20 min (Scheme 2, (6)). When the sulfide 5a was separately
added under the standard conditions, the desired product 3aa
was obtained in 86% yield, which suggested the reaction
proceeded via sulfide oxidation mechanism (Scheme 2, (7)).
Scheme 3 Possible reaction pathway.
Conclusions
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Y.-L. Zhu, W.-J. Hao, A.-F. Wang, D.-C. Wang, F. Liu, P. Wei, S.-J. Tu and B.
In summary, an operationally simple and efficient visible-
light-induced method has been successfully established for the
synthesis of unsymmetrical sulfoxides from aryldiazo sulfones
and thiols in air. A library of structurally diverse sulfoxides with
favorable functionalities was obtained in good yields from
simple and readily-available starting materials. This reaction
has the following features such as operation simplicity,
environmentally begin oxidant, high selectivity, and catalyst-
and additive-free conditions, which make this protocol highly
attractive in organic synthesis. Further investigation of the
detailed reaction mechanism and synthetic application are
ongoing.
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This work was supported by the Natural Science Foundation
of Shandong Province (ZR2018MB009), the International
Cooperation Project of Qinghai Province (2018-HZ-806; 2017-
HZ-806), the Qinghai key laboratory of Tibetan medicine
research (2017-ZJ-Y11), and the National Natural Science
Foundation of China (No. 21302109).
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Page 5 of 5
Green Chemistry
View Article Online
DOI: 10.1039/C9GC00222G
O2 (Air)
O
S
R1
3 W blue LEDs
R2
N2SO2Me
+
R2 SH
R1
CH3CN/H2O (1:1)
rt
27 examples
simple operation
photocatalyst-free
high selectivity
broad substrate scope
environmentally-begin oxidant
A facile visible-light-driven method has been developed to construct sulfoxides from aryldiazo
sulfones and thiols in air under photocatalyst-free conditions.
.