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A general electron donor–acceptor complex for

Cite this: Chem. Sci., 2022, 13, 5659
photoactivation of arenes via thianthrenation†
Kai Sun, a Anzai Shi,a Yan Liu,b Xiaolan Chen, *a Panjie Xiang,a Xiaotong Wang,a
Open Access Article. Published on 14 april 2022. Downloaded on 12.07.2022 15.16.04.
All publication charges for this article

have been paid for by the Royal Society Lingbo Qua and Bing Yu *a
of Chemistry
General photoactivation of electron donor–acceptor (EDA) complexes between arylsulfonium salts and
1,4-diazabicyclo[2.2.2]octane with visible light or natural sunlight was discovered. This practical and
efficient mode enables the production of aryl radicals under mild conditions, providing an unrealized
opportunity for two-step para-selective C–H functionalization of complex arenes. The novel mode for
generating aryl radicals via an EDA complex was well supported by UV-vis absorbance measurements,
nuclear magnetic resonance titration experiments, and density functional theory (DFT) calculations. The
method was applied to the regio- and stereo-selective arylation of various N-heterocycles under mild
Received 2nd March 2022
Accepted 14th April 2022
conditions, yielding an assembly of challengingly linked heteroaryl–(hetero)aryl products. Remarkably,
the meaningful couplings of bioactive molecules with structurally complex drugs or agricultural
DOI: 10.1039/d2sc01241c
pharmaceuticals were achieved to display favorable in vitro antitumor activities, which will be of great
rsc.li/chemical-science value in academia or industry.
Some elegant methods for photocatalytic generation of aryl

Introduction radicals have been reported.8 Very recently, it has been reported
Aryl radicals have proven to be versatile synthetic intermediates that sulfonium salts9 offer a feasible transformative platform for
in organic synthesis, displaying an important role in materials the late-stage functionalization of complex scaffolds. In partic-
science, agricultural chemistry, and especially pharmaceutical ular, triarylsulfonium salts derived from aromatic C–H bonds
chemistry.1 Classically, the generation of aryl radicals depends are promising candidates for photocatalytic organic trans-
heavily on the reduction of aromatic halides by AIBN/n-Bu3SnH formations. However, direct photochemical activation of triar-
or energy-intensive diazonium salts by transition metal reduc- ylsulfonium salts requires strong energy such as ultraviolet
tants.2 The oxidation of arylhydrazines and boronic acids light.10 The high energy of ultraviolet light will destroy more
emerged as an alternative to access aryl radicals in the presence chemical bonds, resulting in low selectivity. Moreover, special
of strong oxidants.3 However, site-selective synthesis of these light sources and equipment, such as high-pressure mercury
active precursors from the corresponding arenes is chal- lamps, lamp boxes, quartz reactors, etc., are usually required.
lenging.4 The range of substrates is limited to simple arenes in Recently, some elegant visible-light mediated activations of
most of the reported systems. Further disadvantages of these triarylsulfonium salts have been reported.11 For example, the
conventional reactions include the employment of toxic or Ritter group disclosed an elegant arylation method of aryl
expensive reagents and harsh oxidants (or reductants). There- sulfonium salts using the iridium complex as the photocatalyst
fore, the development of sustainable approaches for the (Scheme 1a).12 The Procter group reported a metal-free strategy
generation of aryl radicals that can exploit more general for formal C–H/C–H cross-couplings using 10-phenyl-
precursors without harsh oxidants or reductants would be phenothiazine as the optimal photocatalyst (Scheme 1b).13
highly desirable. These strategies rely on the employment of an exogenous pho-
Photocatalysis,5 which directly converts sustainable solar tocatalyst that harvests the energy of visible light to activate
energy into chemical energy,6 now emerges as a promising triarylsulfonium salts for the generation of aryl radicals under
technology to achieve diverse organic transformations in an mild reaction conditions.
environmentally friendly and energy-saving methodology.7 Photoinduced intermolecular charge transfer through the
association of an electron-donating substrate (D) and an elec-
a
Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou
tron acceptor molecule (A) via noncovalent interactions is a well-
450001, China. E-mail: chenxl@zzu.edu.cn; bingyu@zzu.edu.cn known process in photochemistry (Scheme 1c).14 Although each
b
Henan International Joint Laboratory of Rare Earth Composite Material, College of component itself (D or A) might not absorb visible light, the
Materials Engineering, Henan University of Engineering, Zhengzhou 451191, China molecular aggregate formed between the donor and acceptor
† Electronic supplementary information (ESI) available. See molecules in the ground state establishes a new charge-transfer
https://doi.org/10.1039/d2sc01241c
© 2022 The Author(s). Published by the Royal Society of Chemistry Chem. Sci., 2022, 13, 5659–5666 | 5659
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Results and discussion

As an azapyrimidinone analog of uracil, azauracil is a promising
microbiological inhibitor that has been widely studied by
chemists and pharmacists.19 In particular, the ribonucleosides

of 6-azauracil display signicant antiviral, antitumor, and
antifungal activities. New synthetic methods that enrich the
structural diversity of azauracils and nucleosides would signif-
icantly advance research in this area. We hypothesized that
electron-decient arylthianthrenium salts can serve as electron
acceptors, forming EDA complexes with tertiary amines. This
scheme provides an unrealized opportunity to access aryl radi-

cals for the alkylation of azauracils and nucleosides. The
feasibility of our hypothesis was evaluated by selecting toluene
as a model substrate to produce aryl thianthrenium salt 2 to
react with 2,4-dibenzyl-1,2,4-triazine-3,5(2H,4H)-dione (1) for
the synthesis of 2,4-dibenzyl-6-(p-tolyl)-1,2,4-triazine-
3,5(2H,4H)-dione (3) (Table 1). Initially, various commercially
available tertiary amines, including N,N,N0 ,N0 -tetramethylethy-
lenediamine (TMEDA), 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU), 4-dimethylaminopyridine (DMAP), Et3N, 1,1,3,3-tetra-
methylguanidine (TMG), and 1,4-diazabicyclo[2.2.2]octane
(DABCO) (entries 1–6 in Table 1) were investigated. All of these
Scheme 1 Photocatalytic arylation of aryl sulfonium salts.
Table 1 Optimization of the reaction conditionsa

band (hnCT) related to single electron transfer (SET) from the
donor to the acceptor, enabling the ability for absorption of
visible light.15 Upon light irradiation, the SET events in the
electron-donor–accepter (EDA) complex can generate reactive
open-shell intermediates, which act as valuable synthons for
novel synthetic routes under mild conditions.16 In 2021, the Shi
group disclosed the generation of alkyl radicals from EDA
complexes between alkyl thianthrenium salts and the B2cat2- Entry Base Solvent Yield (%)
$DMA adduct.17 During the preparation of our manuscript, the
1 TMEDA MeCN 42
Procter group described the use of photoactive EDA complexes 2 DBU MeCN 50
between arylsulfonium and triarylamines for the production of 3 DMAP MeCN 32
aryl radicals, leading to the formation of alkylation and cyana- 4 Et3N MeCN 50
tion of arenes.18 Such irradiation-induced intermolecular 5 TMG MeCN 59
6 DABCO MeCN 72
charge transfer would provide fresh opportunities for gener-
7 Triphenylamine MeCN Trace
ating aryl radicals from arylthianthrenium salts. This virtually 8 Tri-p-tolylamine MeCN 21
unexplored approach can signicantly expand the synthetic 9 PPh3 MeCN N.D
toolbox of modern chemists. 10 Tricyclohexylphosphine MeCN N.D
Herein, we provide a practical approach for the photo- 11 DABCO DMSO 57
12 DABCO Acetone 61
catalytic generation of aryl radicals from EDA complexes
13 DABCO DCM 32
between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane 14 DABCO DMF Trace
(DABCO), enabling the preparation of high-value-added (hetero) 15 DABCO EtOH Trace
biaryls under mild conditions (Scheme 1d). Through this 16 DABCO DCE 40
simple strategy, bioactive molecules can be meaningfully 17 DABCO THF 21
18b DABCO MeCN 52
coupled with structurally complex drugs or agricultural phar-
19c DABCO MeCN 82
maceuticals. The resulting compounds display favorable in vitro 20d — MeCN N.D
antitumor activities, providing great value in academia or 21e DABCO MeCN N.D
industry. Moreover, this novel mode for generating aryl radicals a
Reaction conditions: 1 (0.1 mmol), 2 (0.2 mmol), base (2 equiv.), and
via EDA complexes was comprehensively studied through an appropriate solvent (1.5 mL) were irradiated with a 10 W blue LED
UVvis absorbance measurements, nuclear magnetic reso- (430 nm) at room temperature under a N2 atmosphere for 12 h. Yields
were determined by 1H NMR using 1,1,2,2-tetrachloroethane as an
nance (NMR) titration experiments, and density functional
internal standard based on 1. N.D ¼ not detected. b DABCO (1 equiv.).
theory (DFT) calculations. c
DABCO (3 equiv.). d No base. e In the dark.
5660 | Chem. Sci., 2022, 13, 5659–5666 © 2022 The Author(s). Published by the Royal Society of Chemistry
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tertiary amines effectively promoted the reaction, and the 17). Unfortunately, these attempts failed to improve the yield,
desired product 3 was obtained in 72% yield when DABCO was and no positive results were obtained. Next, the dosage of
employed (entry 6). However, when triphenylamine or tri-p-tol- tertiary amine was optimized to further improve the reaction
ylamine was employed as the electron-donating reagents, the efficiency (entries 18 and 19). The best dosage was 3 equiv. of
yield of product 3 was signicantly reduced (entries 7 and 8). DABCO, which afforded the desired product 3 in 82% yield. The
Moreover, no desired product could be detected when PPh3 or control experiments conducted in the absence of tertiary
tricyclohexylphosphane was used instead of tertiary amines amines and visible light gave no desired product, indicating the
(entries 9 and 10). Then, a series of other solvents, including important roles of tertiary amine and light in this trans-
dimethyl sulfoxide (DMSO), acetone, dichloromethane (DCM), formation (entries 20 and 21). Furthermore, additional experi-
dimethylformamide (DMF), ethanol (EtOH), 1,2-dichloroethane ments showed that the donor loading could be decreased below
(DCE), and tetrahydrofuran (THF), were screened (entries 11– 1 equivalent by adding other bases (for details, see Table S1†).
Scheme 2 Substrate scope of the alkylation of azauracils and nucleosides.
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Having optimized the reaction conditions, we then turn our a suitable substrate to furnish the desired product 58 in 34%
attention to examining the generality of our practical protocol. yield. To explore the arene generality of the protocol, various
Initially, arenes bearing a wide range of functional groups were electron-rich, neutral, and electron-poor arenes were reacted
reacted with 2,4-dibenzyl-1,2,4-triazine-3,5(2H,4H)-dione (1) with N-methylquinoxalin-2(1H)-one under the optimized reac-
(Scheme 2). To our delight, all of these arenes were suitable tion conditions. Remarkably, the functional groups –Me, –Et,
substrates for the two-step site-selective C–H arylation reaction, –Bn, –OAc, –Ph, –OMe, –OPh, –F, –Cl, –Br, –CN, –CHO,
obtaining the desired products 3–19 in moderate to good yields –COOMe, and –COCH3 were transformed into their corre-
(44–82%). It is worth emphasizing that various functional sponding products 59–82 in average to good yields, highlighting
groups were tolerated in these cases, and some sensitive func- the compatibility of the protocol with a wide range of functional
tional groups such as –CHO, –CN, and –COCH3 were compatible groups. Likewise, when aniline participated in this reaction,
with the transformation. The acid-sensitive free amino group product 83 was generated in 65% yield, in which tri-
uoroacylation of the free amino group occurs. The scope of the
was triuoroacylated to product 19 in 68% yield. The straight-

forward and selective modication of biorelevant compounds protocol was further extended to facile late-stage functionali-
are of importance in research and development campaigns.20 zation of valuable scaffolds containing drug-like molecules and
These conditions can be used in the late-stage diversication of natural isolates. For example, quinoxalin-2(1H)-ones containing
drugs and agricultural pharmaceuticals, such as the multi-use o-vanillin, p-vanillin, zingerone, ibuprofen, and isoxepac were
insecticide pyriproxyphen, the fungicide boscalid, and atom- selectively arylated to the desired products 84–88 in 48–81%
oxetine for the treatment of attention decit and hyperactivity yields. Neracetam, pyriproxyphen, urbiprofen methyl ester,
disorder, affording the corresponding products 20–22 in satis- boscalid, and atomoxetine were all efficient arylation reagents
factory yields (53–71%). Flurbiprofen methyl ester, a drug in this two-step C–H alkylation reaction to produce products 89–
derivative, was also amenable to this transformation, affording 93, demonstrating the utility of this transformation. Finally, the
product 23 in 72% yield. Aerward, the scope of 6-azauracils application of this methodology for the preparation of antimi-
was assessed. Gratifyingly, N,N0 -disubstituted 6-azauracils were crobial and antitumor agent 94 was achieved, and a 72% yield of
smoothly arylated with thianthrenium salt 2, affording the the desired product was obtained. Likewise, in a condition-
corresponding products 24–26 in satisfactory yields (57–73%). based sensitivity assessment, low light intensity, high oxygen
Moreover, the new anticoccidial drug diclazuril was also concentrations, and the DABCO amount were the main factors
compatible with this efficient methodology, giving the product inuencing the preparation reproducibility of product 41 (for
27 in 53% yield. It is noteworthy that convenient C(sp2)–H ary- details, see the ESI†).
lation of 6-azauridine nucleosides was successfully achieved, Encouraged by the above results, we further examined the
furnishing the arylated 6-azauridine nucleosides 28–34 in generality of the proposed protocol by screening other simple
moderate yields (47–71%). In these cases, the free secondary yet signicant (hetero)aryl cycles (Scheme 4). To our delight,
N–H group in the 6-azauridine nucleosides was tolerated with coumarin, 1-(uoromethyl)cinnolin-4(1H)-one, and 2-phenyl-
no signicant effects on the reaction efficiency. Additionally, imidazo[1,2-a]pyridine were successfully arylated under the
this protocol provides a feasible way for the effective coupling of optimized reaction conditions, producing the corresponding
6-azauridine nucleosides and pharmaceuticals, leading to the products 95-97 in acceptable yields. Moreover, 3-methylene-1-
corresponding nucleoside derivatives 35–39 in moderate yields phenylpyrrolidine-2,5-dione, which could be transformed into
(41–63%). Diclazuril was also coupled with boscalid to afford 3-methyl-1-phenyl-1H-pyrrole-2,5-dione in the presence of
the corresponding product 40 in 38% yield. More importantly, base,23 was a suitable substrate to access product 98 in 36%
in all of the above cases, thianthrene was recovered by separa- yield. Additionally, this method was also applied to the direct
tion and reused in subsequent cycles. Additionally, the model C–H arylation of tangeretin and 1,3,5-trimethoxybenzene,
reaction efficiency of product 3 was investigated under different leading to the formation of desired products 99 and 100 in 36%
reaction parameters.21 In a comprehensively condition-based and 61% yields, respectively. Unfortunately, some other (hetero)
sensitivity assessment, this photocatalytic transformation was aromatic cycles, including pyridine, quinoline, benzothiazole,
sensitive to low light intensity and high oxygen concentrations, benzoxazole and indole were not suitable substrates for this
which was generally tolerant toward the substrate concentra- transformation, and no desired products could be detected (for
tion, reaction temperature, water, and scale (see the radar details, see Scheme S1†).
diagram in Scheme 2 and the ESI† for details). To clarify the practicality of these transformations, the gram-
The proposed photoactivation of arenes via thianthrenation scale synthesis of products 3 and 41 was performed on 4 mmol
was then applied to the arylation of quinoxalin-2(1H)-ones and 5 mmol scales, respectively. To our delight, the reactions
(Scheme 3), which play a signicant role in antimicrobial proceeded smoothly to provide the desired products with no
compounds, antitumor agents, and semiconductors.22 Through signicant reduction in yields only by increasing the light
this protocol, various quinoxalin-2(1H)-ones bearing different intensity and reaction time (Scheme 5). Furthermore, natural
functional groups afforded the corresponding products 41–57 sunlight-driven experiments were performed, leading to the
with excellent site selectivity and reactivity. Owing to the mild formation of substantial amounts of products 3 and 41 in 79%
reaction conditions, sensitive alkenyl, alkynyl, and hydroxy and 76% yields, respectively. A one-pot sequence was also
groups were well tolerated under the optimized conditions (44– explored, and product 3 could be obtained in 37% yield (for
46). Notably, N-unsubstituted quinoxalin-2(1H)-one was also details, see the ESI†).
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Scheme 3 Substrate scope for the arylation of quinoxalin-2(1H)-ones.
Importantly, the in vitro antitumor activities of the synthetic uorouracil (5-FU, 13.7 mM), indicating the potential of our
compounds 37 and 92 were evaluated in Ramos cells. The method in the development of novel drugs.
results indicated that compounds 37 and 92 exhibited excellent To get deep insight into the reaction mechanism, some
antitumor activities (Fig. S7†). In the aspect of anti-lymphoma radical trapping experiments were conducted (Scheme 6). When
activity, the IC50 values of compounds 37 and 92 against the radical scavenger (2,2,6,6-tetramethylpiperidin-1-yl)
Ramos cells are slightly lower than that of the approved drug oxidanyl (TEMPO) or 1,1-diphenylethylene was added to the
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Scheme 6 Control experiments.
Scheme 4 Screening of other (hetero)aromatic cycles. (a) Reaction

conditions: (hetero)aromatic cycle (0.1 mmol) was reacted with was also severely inhibited by TEMPO, 1,1-diphenylethylene, or
thianthrenium salt (0.2 mmol) in the presence of DABCO (3 equiv.) CuCl (for details, see the ESI†).
under 10 W blue LED irradiation. (b) 3-Methylene-1-phenylpyrrolidine- The formation of the EDA complex was conrmed in addi-
2,5-dione (0.1 mmol) is used as a substrate to react with thianthrenium tional mechanism investigations (Fig. 1). When DABCO was
salt (0.2 mmol) in the presence of DABCO (3 equiv.) under 10 W blue
LED irradiation. (c) Thianthrenium salt (0.1 mmol) was reacted with
added to a solution of arylthianthrenium salt 2 in CH3CN, the
(hetero)aromatic cycle (10 equiv.) in the presence of DABCO (3 equiv.) solution developed a marked yellow color. The UV-vis absor-
under 10 W blue LED irradiation. bance experimental results showed that the absorption peaks of
the DABCO and arylthianthreniumsalt 2 mixture appeared at
430–460 nm, while those of control groups can only be observed
in the near UV-region. This might be caused by the formation of
a new EDA molecular aggregate. Moreover, 1H NMR titration
experiments and a Job's plot analysis conrmed the formation
of a 1 : 1 complex between the arylthianthrenium salt 2 and
DABCO. The binding constant Ka of complexation was 1.04 M1
in CDCl3 (for details, see the ESI†). Additionally, DFT calcula-
tions were carried out to better understand the intermolecular
charge transfer between arylthianthrenium salt 2 and DABCO.
In the equilibrium structure, the distance d of the N/S
Scheme 5 Synthetic applications.
model reaction, the reactions were severely inhibited. Moreover,

CuCl was also proven to be an effective inhibitor of this trans-
formation. All of these results indicated the possible involve-
ment of a radical pathway. Additionally, the reaction mixtures
were analyzed by high-resolution mass spectrometry (HRMS),
and the adducts 101 and 102 were successfully detected,
respectively. These results strongly support the generation of Fig. 1 (a) UV-Vis absorption spectra of reactant mixtures recorded in
CH3CN in 1 mm path-length quartz cuvettes, and visual appearance of
aryl radicals in the photocatalytic transformation, which might
the separate reaction components and the colored EDA complex
be initiated by the photo-activated EDA complexes between between compound 2 and DABCO. (b) Calculated bond distances of
arylsulfonium salts and DABCO. The preparation of product 41 arylsulfonium salt 2 and DABCO. (c) Calculated HOMO and LUMO of
the EDA complex.
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arenes to aryl radicals via thianthrenation will facilitate further

arylation processes, providing meaningful compounds under
mild reaction conditions.
Data availability
The data that support the ndings of this study are available in
the ESI† or on request from the corresponding author.
Author contributions
K. S., X. L. C. and B. Y. designed the subject and guided the

experiments throughout. K. S., A. Z. S., Y. L., P. J. X. and X. T. W.
conducted the organic synthesis and characterization. Y. L.
conducted the DFT calculations, and K. S. performed the in vitro
antitumor activity analysis. K. S., L. B. Qu and B. Y. completed
Scheme 7 Proposed mechanism.
the article writing together.
interactions was 2.26 Å, shorter than the summed van der Waals Conflicts of interest
radii of the two interacting atoms (3.78 Å).24 The binding energy There are no conicts to declare.
was calculated to be 3.73 kcal mol1, implying a feasible
interaction between the arylthianthrenium salt 2 and DABCO.
The low energy gap (0.64 eV) between the highest occupied Acknowledgements
molecular orbital (HOMO) and the lowest unoccupied molec- We acknowledge the nancial support from the National
ular orbital (LUMO) indicated a favorable electron-transfer Natural Science Foundation of China (21971224, 22071222, and
process under visible light irradiation. 22171249), the Key Research Projects of Universities in Henan
Based on the above observations and previous reports,25 Province (21A150053), the Natural Science Foundation of
a plausible mechanism containing EDA complexes for the Henan Province (202300410375), China Postdoctoral Science
generation of aryl radicals was proposed (Scheme 7). Initially, Foundation (2021M692906) and Henan Postdoctoral Founda-
DABCO combines with the aryl thianthrenium salt 2 to generate tion (202003014).
the EDA complex, which produces the aryl radical 103, thian-
threne, and DABCOc+ (106). Aerward, the addition of aryl
radical 103 to the C]N bond of 2,4-dibenzyl-1,2,4-triazine- Notes and references
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Chemical

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A general electron donor–acceptor complex for

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Some elegant methods for photocatalytic generation of aryl

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Results and discussion

chemists and pharmacists.19 In particular, the ribonucleosides

scheme provides an unrealized opportunity to access aryl radi-

Table 1 Optimization of the reaction conditionsa

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Scheme 2 Substrate scope of the alkylation of azauracils and nucleosides.

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was triuoroacylated to product 19 in 68% yield. The straight-

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Scheme 3 Substrate scope for the arylation of quinoxalin-2(1H)-ones.

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Scheme 6 Control experiments.

Scheme 4 Screening of other (hetero)aromatic cycles. (a) Reaction

Scheme 5 Synthetic applications.

model reaction, the reactions were severely inhibited. Moreover,

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arenes to aryl radicals via thianthrenation will facilitate further

K. S., X. L. C. and B. Y. designed the subject and guided the

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