Ethylene Glycol: A Green Solvent for Visible Light-Promoted Aerobic Transition Metal-Free Cascade Sulfonation/Cyclization Reaction

Article abstract of DOI:10.1002/adsc.202000233

With ethylene glycol as a green solvent, a general transition metal-free photocatalytic system using 9-mesityl-10-methylacridinium perchlorate (Acr⁺?Mes ? ClO₄^?) as catalyst was developed for the synthesis of sulfone-conta

Full text of DOI:10.1002/adsc.202000233

Title: Ethylene Glycol: A Green Solvent for Visible Light-Promoted
Aerobic Transition Metal-Free Cascade Sulfonation/Cyclization
Reaction
Authors: Yuqin Jiang, Jing Li, Zhi-Wen Feng, Guiqing Xu, Xin Shi,
Qing-Jie Ding, Wei Li, Chun-Hua Ma, and Bing Yu
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000233
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10.1002/adsc.202000233
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.202000233
Ethylene Glycol: A Green Solvent for Visible Light-Promoted
Aerobic Transition Metal-Free Cascade Sulfonation/Cyclization
Reaction
Yu-Qin Jiang,a Jing Li,a Zhi-Wen Feng,a Gui-Qing Xu,a Xin Shi,a Qing-Jie Ding,a Wei
Li,a Chun-Hua Ma,a* and Bing Yub*
a.
Henan Engineering Laboratory of Chemical Pharmaceuticals & Biomedical Materials, Collaborative Innovation Center
of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and
Reactions of Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University,
Jianshedong Road No. 46, Xinxiang 453007, P. R. China. E-mail: 2016007@htu.edu.cn
b. Green Catalysis Center, College of Chemistry, Zhengzhou University, Kexue Road No. 100, Zhengzhou 450001, P. R.
China. E-mail: bingyu@zzu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
require transition metal catalysts/additives in volatile
organic solvents under elevated temperature.[9] Therefore,
the development of a transition metal-free photocatalytic
approach for the cascade sulfonation/cyclization reactions
in a green solvent under room temperature is highly
attractive.
Abstract. With ethylene glycol as a green solvent, a
general transition metal-free photocatalytic system using 9-
-
mesityl-10-methylacridinium perchlorate (Acr+–Mes·ClO4
) as catalyst was developed for the synthesis of sulfone-
containing heterocycles including thioflavones, oxindoles,
and quinoline-2,4(1H,3H)-diones through the cascade
sulfonation/cyclization reactions under the irradiation of
blue light at room temperature.
Ethylene glycol (EG) is an abundant resource in
chemical industry, which can be produced from renewable
biomass.[10] Moreover, EG is also an odourless, non-
volatile, low toxic solvent, which has enormous
applications in various industrial processes.[11] With our
continuing interest in green chemistry and tandem
reactions,[12] we herein disclosed that EG could be an
excellent green solvent for photocatalytic cascade
sulfonation/cyclization reactions using 9-mesityl-10-
Keywords: Photocatalysis; Green solvent; Sulfonation;
Cyclization; Heterocycles
Visible light-promoted reactions have gained huge
attention in the past decade, which are generally conducted
under mild reaction conditions and provide high efficiency
-
methylacridinium perchlorate (Acr+–Mes·ClO4 ) as a
and selectivity.[1] Therefore,
a
large number of
transition metal-free photocatalyst in the presence of
K2S2O8 or molecular oxygen as oxidant (Scheme 1).
Through this versatile catalytic system, various sulfone-
containing heterocycles including thioflavones, oxindoles,
and quinoline-2,4(1H,3H)-diones, were successfully
constructed under mild conditions.
photocatalytic systems have been developed for the
construction of valuable products.[2] In most of the reported
photocatalytic systems, conventional volatile organic
solvents are often applied as the reaction medium, which
would produce large amount of wastes after the
reactions.[3] From the standpoint of sustainable chemistry,
the exploration of non-volatile and nontoxic green solvents
for photocatalytic reactions is highly desirable.[4]
Sulfone-containing compounds play significant roles in
the field of agrochemicals, pharmaceuticals and material
science. Consequently, enormous efforts have been
devoted to the construction of sulfone-containing scaffolds
in the past decades.[5] Among the reported procedures,
sulfonyl radical triggered cascade sulfonation/cyclization
reaction is one of the most effective strategies to construct
the valuable heterocyclic scaffolds and introduce the
sulfonyl group simultaneously.[6] For example, the copper-
catalyzed sulfonation/cyclization reaction for the synthesis
of 3-sulfonated indenones from sulfonyl hydrazides was
independently reported by Jiang’s group[7] and our group[8].
Among those reports, typical reaction conditions still
Scheme 1. Transition metal-free photocatalytic cascade
sulfonation/cyclization reaction in ethylene glycol
For the initial investigation, methylthiolated alkynone 1a
and benzenesulfonyl hydrazide (PhSO2NHNH2) 2a were
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000233
Advanced Synthesis & Catalysis
presence of 2a (2 equiv) and K2S2O8 (2 equiv) (entry 16).
Importantly, when the reaction was carried out under O2
balloon, the product 3a could be isolated in 65% yield (entry
17), which was improved to 84% by increasing the reaction
time from 12 h to 24 h (entry 18). These results suggested the
molecular oxygen was a green oxidant in this transformation.
Moreover, the control experiments without either Acr+–
Mes·ClO4 or visible light did not give any product (entries 19
and 20), demonstrating the photocatalyst and light irradiation
play significant roles in this process. Therefore, the optimal
employed as the reactants for the model reaction using
water as solvent in open air (Table 1). Considering the
solubility of organic photocatalysts in water, the slat Acr+–
-
Mes·ClO4 was firstly applied as photocatalyst for the
screening of various oxidants including tert-butyl
hydroperoxide (TBHP), benzoyl peroxide (BPO), H2O2, di-
tert-butyl peroxide (DTBP), and K2S2O8 (entries 1-5).
Gratifyingly, the desired product sulfonated thioflavone 3a
were observed in all cases, suggesting the photocatalyst
and oxidants were compatible in water. Among them,
K2S2O8 showed the highest activity, delivering 3a in 37%
yield (entry 5). When the reaction was conducted under N2
atmosphere, the yield of 3a was slightly increased (entry
6). Then various organic photocatalysts were surveyed in
the presence of K2S2O8 under N2 atmosphere. For instance,
when eosin Y, 4CzIPN, uranine, rhodamine B, methylene
blue, and rose bengal were employed, only poor yields of
3a were observed (entries 7-12). These results indicate that
-
Table
2.
Substrate
scope
of
the
cascade
sulfonation/cyclization reactiona
-
Acr+–Mes·ClO4 is a unique photocatalyst for the cascade
sulfonation/cyclization reaction in water. To further improve
the yield, several green solvents like dimethyl carbonate
(DMC), polyethylene glycol (PEG600), and ethylene glycol
(EG) were evaluated under N2 atmosphere (entries 13-15). To
our surprise, 82% yield of 3a were given when the reaction
was performed in EG (entry 15). Further optimization
revealed that the yield of 3a was almost retained when the
-
reaction was catalyzed by 3 mol% of Acr+–Mes·ClO4 in the
Table 1. Optimization of reaction conditionsa
Catalyst
(5 mol%)
Oxidant
(equiv)
TBHP (2)
BPO (2)
Yield
(%)
25
34
25
29
37
42
15
trace
trace
trace
trace
N.R.
8
26
82
81
65
Entry
Solvent
-
-
-
-
-
-
1
2
3
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Eosin Y
4CzIPN
Uranine
Rhodamine B
Methylene blue
Rose bengal
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
DMC
PEG600
EG
H2O2 (2)
4
DTBP (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
K2S2O8 (2)
O2 balloon
O2 balloon
K2S2O8 (2)
K2S2O8 (2)
5
6b
7b
8b
9b
10b
11b
12b
13b
14b
15b
16b,c
17d
18d,e
19b
20b,f
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
Acr+–Mes·ClO4
––
-
-
-
-
-
-
EG
EG
EG
EG
84
N.R.
N.R.
Acr+–Mes·ClO4
EG
-
a Reaction conditions: 1a (0.2 mmol), 2a (3 equiv), catalyst (5
mol%), oxidant (2 equiv), solvent (2 mL), room temperature,
blue LEDs, 12 h, in air. Isolated yields were given based on 1a.
a
Reaction conditions A: 1 (0.2 mmol), 2 (2 equiv), Acr+–
Mes·ClO4- (3 mol%), K2S2O8 (2 equiv), EG (2 mL), blue LEDs,
b
c
b
Reaction under N2 atmosphere. 2a (2 equiv), 3 mol% of
12 h, under nitrogen. Isolated yields were given based on 1.
catalyst were used. d 3 mol% of catalyst were used. e 24 h.
Without light.
f
Reaction conditions B: 1 (0.2 mmol), 2 (3 equiv), Acr+–
-
Mes·ClO4 (3 mol%), EG (2 mL), blue LEDs, 12 h, under
oxygen balloon. Isolated yields were given based on 1.
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000233
Advanced Synthesis & Catalysis
conditions for this photocatalytic reaction were established as
good yields (39-70%). The arylsulfonyl hydrazides 2 bearing
an electron-donating group (i.e., 4-Cl) and an electron-
withdrawing group (i.e., 4-tBu) were also well tolerated.
follow: 1a (0.2 mmol), 2a (2 equiv or 3 equiv), Acr+–
-
Mes·ClO4 (3 mol%) as catalyst, K2S2O8 (2 equiv) (conditions
A) or O2 (1 atm) (conditions B) as oxidant, ethylene glycol (2
mL) as solvent, at room temperature under the irradiation of
blue light (λmax = 460 nm).
To get a deeper insight into this photocatalyzed cascade
sulfonation/cyclization
reaction,
the
Stern-Volmer
fluorescence quenching experiments were conducted by
-
With the optimal conditions in hand, we then investigated
the scope and generality of this photocatalytic system for the
cascade sulfonation/cyclization reaction to synthesize diverse
mixing the photocatalyst Acr+–Mes·ClO4 with the substrates
1a and 2a, respectively. As shown in Figure 1, the
luminescence quenching effect was observed when 1a was
added to the solution of photocatalyst. Additionally, the linear
relationship between I0/I and the concentration of 1a
confirmed that 1a was an effective quencher of the excited
sulfonated thioflavones
3
from the corresponding
methylthiolated alkynones 1 and arylsulfonyl hydrazides 2. As
shown in Table 2, the methylthiolated alkynones containing
electron-donating groups (e.g., 4-Me, 4-Et, 3-Me) and the
electron-withdrawing groups (e.g., 4-Cl, 4-Br, 2-Br, 4-CN)
reacted well with benzenesulfonyl hydrazide 2a under
conditions A, affording the corresponding sulfonated
thioflavone products 3b-3h in moderate to good yields (45-
85%). For the reaction with p-toluenesulfonyl hydrazide under
conditions A, various electron-donating groups and electron-
withdrawing groups on the phenyl ring of methylthiolated
alkynones could also be tolerated, giving the corresponding
products 3i-3s in 49-81% yields. Moreover, the substituted
arylsulfonyl hydrazides were also studies under conditions A,
which showed excellent compatibilities with a broad range of
functional groups (e.g., 4-OMe, 4-tBu, 2-Me, 3-Me, 4-F, 4-Cl,
4-Br, 4-I, 3-F, and 1-naphthyl), providing the corresponding
products 3t-3ac in good to excellent yields. These results
demonstrated that the electronic effects were not obvious
under conditions A. Additionally, typical substrates were also
applied under conditions B. In the cases of 3b, 3e, 3i, 3u and
3y, moderate to good yields were also obtained, albeit lower
than that of conditions A.
-
state of Acr+–Mes·ClO4 (see the Supporting Information).
6000
cat.
5000
4000
3000
2000
1000
0
cat. + 2a
cat. + 1a
400
500
600
700
Wavelength (nm)
Figure 1. Fluorescence quenching experiments
Moreover, when the radical scavenger 2,2,6,6-
tetramethylpiperidinyl-1-oxyl (TEMPO) was added to the
reaction of 1a and 2b under the standard conditions A, no
desired product 3i was generated, indicating that this
photocatalytic reaction might involve a radical pathway
(Scheme 3).
Given that the photocatalytic system tolerates the wide
scope of functional groups for the synthesis of sulfonated
thioflavones, we then extend this sustainable catalytic system
to the synthesis of different sulfonated heterocycles under
conditions A (Scheme 2). To our delight, the substrates N-
aryl-N-methylmethacrylamide 4 and N-(2-cyanophenyl)-N-
methylmethacrylamide 5 were applicable under the standard
conditions giving the corresponding sulfonated oxindoles 6
and sulfonated quinoline-2,4(1H,3H)-diones 7 in moderate to
Scheme 3. Control experiment
Based on the above results and previous reports,[13]
a
plausible mechanism was proposed. As described in Scheme
4, the long-lived electron-transfer (ET) state (Acr•–Mes•+) was
firstly generated from the ground state Acr+–Mes under the
irradiation of visible light.[14] Due to the high oxidizing ability
of ET state (Acr•–Mes•+), the substrate 1 was oxidized to the
corresponding radical cation 1•+, furnishing the radical Acr•–
•
Mes. On the other hand, the arylsulfonyl radical (ArSO2 ) was
produced from the arylsulfonyl hydrazide 2 in the presence of
•
K2S2O8.[15] Then the radical ArSO2 reacted with Acr•–Mes via
a single-electron transfer (SET) process to produce the
-
arylsulfinate anion (ArSO2 ) and regenerate the ground state
-
Acr+–Mes. Subsequently, the combination of ArSO2 and 1•+
gave the radical intermediate 8, which was converted into the
final product 3 through an intramolecular cyclization by
releasing
a methyl radical. It is speculated that the
employment of polar ethylene glycol as reaction medium
might be advantageous to stabilize the ionic intermediates and
thus facilitates the cascade sulfonation/cyclization reaction.
Furthermore, the gram scale synthesis was also conducted
under the standard conditions A. Unfortunately, only 42%
yield of the desired product 3a was obtained (for details see
the supporting information). This result is presumably owing
Scheme 2. Synthesis of sulfonated oxindoles and sulfonated
quinoline-2,4(1H,3H)-diones
3
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10.1002/adsc.202000233
Advanced Synthesis & Catalysis
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Scheme 4. The proposed mechanism
In conclusion, we have developed a general and practical
photocatalytic
system
for
various
cascade
sulfonation/cyclization reaction using ethylene glycol as a
unique and green medium. With this versatile transition
metal-free procedure, sulfone-containing heterocycles
including thioflavones, oxindoles, and quinoline-2,4(1H,3H)-
diones, were successfully constructed under the irradiation of
blue light at room temperature. It is speculated that the polar
ethylene glycol might be critical for the stabilization of ionic
intermediates in the reactions. Further studies employ this
photocatalytic system for other organic transformations under
visible light are being pursued in our laboratory.
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Experimental Section
General procedures for the synthesis of 2-sulfonylated
thioflavones: In a 25 mL reaction vial with a stirring bar,
methylthiolated alkynone
1
(0.2 mmol), arylsulfonyl
hydrazide 2 (2 equiv), K2S2O8 (2 equiv), and Acr+–Mes·ClO4
(3 mol%) were added. The vial is then evacuated and
backfilled three times with N2, followed by adding ethylene
glycol (2 mL). The mixture was stirred at blue LEDs for 12 h
under nitrogen atmosphere. After the reaction was completed,
the solvent was quenched with water (15 mL), and then the
ethyl acetate (15 mL) was added three times for extraction.
The combined organic layers were dried over anhydrous
Na2SO4. The residue was purified by column chromatography
(silica gel, petroleum ether/ethyl acetate = 6/1) to afford the
desired product 3.
-
Acknowledgements
We acknowledge the financial support from National Natural
Science Foundation of China (21971224), Natural Science
Foundation of Henan Province (162300410182), Key Research
Projects of Universities in Henan Province (20A150006,
20B350001), and Postgraduate Education Reform Project of
Henan Province (2019SJGLX008Y, 2019SJGLX034Y).
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10.1002/adsc.202000233
Advanced Synthesis & Catalysis
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