Trichloroisocyanuric Acid-Promoted Synthesis of Arylselenides and Aryltellurides from Diorganyl Dichalcogenides and Arylboronic Acids at Ambient Temperature

Article abstract of DOI:10.1002/adsc.202100371

A transition-metal-free method for the synthesis of arylselenides and aryltellurides has been established based on the oxidative cross-coupling between diorganyl dichalcogenides and aryl boronic acids. With trichloroisocyanuric acid as an oxidant, the reaction proceeded smoothly to afford the desired products in 45–97% yields at ambient temperature. Three reaction reagents used in this method are stoichiometric and the oxidation by-product isocyanuric acid can be easily isolated and recovered. Besides of arylboronic acids, aryl trifluoroborates and aryl trihydroxyborates salts are also able to perform this transformation. (Figure presented.).

Full text of DOI:10.1002/adsc.202100371

RESEARCH ARTICLE
DOI: 10.1002/adsc.202100371
Trichloroisocyanuric Acid-Promoted Synthesis of Arylselenides
and Aryltellurides from Diorganyl Dichalcogenides and
Arylboronic Acids at Ambient Temperature
Nan Sun,a,* Kai Zheng,a Pengyuan Sun,a Yang Chen,a Liqun Jin,a Baoxiang Hu,a
Zhenlu Shen,a and Xinquan Hua,*
a
College of Chemical Engineering,
Zhejiang University of Technology,
Hangzhou 310032, People’s Republic of China
Phone: (+86)-571-88320103
Fax: (+86)-571-88320103
E-mail: sunnan@zjut.edu.cn; xinquan@zjut.edu.cn
Manuscript received: March 25, 2021; Revised manuscript received: May 24, 2021;
Version of record online: ■■■, ■■■■
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202100371
Abstract: A transition-metal-free method for the synthesis of arylselenides and aryltellurides has been
established based on the oxidative cross-coupling between diorganyl dichalcogenides and aryl boronic acids.
With trichloroisocyanuric acid as an oxidant, the reaction proceeded smoothly to afford the desired products in
45–97% yields at ambient temperature. Three reaction reagents used in this method are stoichiometric and the
oxidation by-product isocyanuric acid can be easily isolated and recovered. Besides of arylboronic acids, aryl
trifluoroborates and aryl trihydroxyborates salts are also able to perform this transformation.
Keywords: arylchalcogens; diorganyl dichalcogenides; aryl boronic acids and derivatives; trichloroisocyanuric
acid; transition-metal-free
Introduction
formation of aryl-chalcogen bonds based on the
oxidative cross-coupling between diorganyl dichalco-
Arylchalcogens, especially arylselenides and aryltellur- genides and arylboronic compounds has attracted
ide, are an important class of organochalcogenium considerable attentions. This is attributed to a large
compounds with broad applications in medicinal degree to the unique features of these two types of
chemistry, material sciences and organic synthesis. For reaction partners, including lower toxicity, ready
instance, arylselenides and aryltellurides are regarded availability, compatibility with wide functional groups,
as useful compounds in drug discovery because of as well as stability towards air and moisture.[8,9] With
their significant biological activities, such as antiox- transition-metal catalysts, such as Cu,[10] Fe,[11] In[12]
idant, antibacterial, antifungal, antiinflammatory, and and Ag,[13] this coupling reaction can be carried out
antitumor.[1] Moreover, some of them have also been with DMSO and/or air as cheap terminal oxidants. A
proven to be as powerful organocatalysts[2] or strongly main troublesome issue of these transition-metal-
electron-donating ligands[3] for various chemical trans- catalyzed protocols is the difficult removal of the
formations, as fluorescentled molecular probes for residual metals from the target products particularly in
detection of biologically active molecules,[4] as pre- pharmaceuticals industry, together with the generation
cursors for synthesis of ionic liquids,[5] and as of a large amount of metal-containing effluents.[14] To
monomers for construction of functionalized polymer overcome this problem, a few Cu-based heterogeneous
materials.[6]
catalysts (Cu nanoparticles or insoluble solid-supported
The versatility and utility of arylchalcogenides Cu salts) have been recently developed,[15] while the
motivated chemists to constantly develop different preparation of these special catalysts is time- and
methods for their synthesis.[7] Among them, the labor-consuming.
Adv. Synth. Catal. 2021, 363, 1–9
1
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
Alternatively, very recently, several research groups Therefore, the exploration of a more efficient, general
disclosed that this oxidative cross-coupling reaction and environment begin transiton-metal-free protocol
can be directly promoted by appropriate chemical for arylchalcogenides synthesis is still attractive and
oxidants without the assistance of transition-metal valuable.
catalysts. For instance, in 2015, Braga[16] firstly
Trichloroisocyanuric acid (TCCA) is a stable, less-
described an I2-catalyzed and DMSO-mediated oxida- expensive, low-toxic and bulky commercially available
tion system for the synthesis of arylsulfides/selenides/ chemicals, commonly used as a bleaching agent,
tellurides from their corresponding dichalcogenides disinfectant, or bactericide in industry. Under appro-
and arylboronic acids under solvent-free conditions at priate reaction conditions, TCCA can in situ release
100 C (Scheme 1a). It was also found that the trans- either chloride cations (Cl+) or chlorine radicals (Cl·),
°
formation can be accelerated by the assistance of MW and thus can be applied in various oxidation and
irradiation. More recently in 2018, Perin and Alves[17] halogenation reactions.[19] Especially, at the end of all
reported that Oxone® as a cheap chemical oxidant can TCCA-involved reactions, its reaction by-product
be used in the reactions of diorganyl diselenides and isocyanuric acid can be recovered to regenerate
ditellurides with arylboronic acids to synthesize TCCA.[20] In this regard, TCCA was regarded as an
°
arylselenides and aryltellurides in dry ethanol at 60 C atom-economic and eco-friendly chemical reaction
(Scheme 1b). Unfortunately, this method was slightly reagent in organic synthesis. In the last few years, the
limited to the electron-rich and non-sterically hindered groups of Silveira,[21] Togni,[22] and Alves[23] succes-
arylboronic acids. At the same year, Zhao[18] reported a sively reported the synthesis of functionalized organo-
BF3·OEt2-catalyzed and DEAD-mediated oxidation chalcogen compounds from diorganyl dichalcogenides
system for the synthesis of arylselenides from diorgan- with TCCA as efficient chemical oxidant. With these
yl diselenides and arylboronic acids, in which the significant advantages, we assumed that TCCA could
reactions were carried out under room temperature be potentially applied as green and efficient chemical
(Scheme 1c). Although above works realized the oxidant for the synthesis of arylchalcogenides from
concept of transition-metal-free alternatives for the diorganyl dichalcogenides and arylboron derivatives.
access of arylchalcogenides from diorganyl dichalco- Herein, we reported our research work on this TCCA-
genides and arylboric acids, they were also suffered promoted reaction, in which a wide range of (hetero)
from more or less limitations, such as, the use of a aryl-aryl, alkyl-aryl selenides and tellurides can be
special equipment, limited substrate scopes and/or the efficiently synthesized in good to excellent yields at
generation of a large amount of wastes after oxidation. ambient temperature (Scheme 1d).
Results and Discussion
Our research was initiated by choosing half equiv. of
diphenyl diselenide (1a) and 4-methylphenyl boronic
acid (2a) as the model substrates to form 4-meth-
ylphenyl phenyl selenide (3aa). In order to verify the
possibility of this coupling reaction, the experiment
was tested with stoichiometric amount of TCCA
(0.33 equiv. based on 2a) as oxidant in methanol. After
°
the mixture was stirred at room temperature (25–30 C)
for 4 h, we were delighted to find that about 68% of
starting material 1a was consumed along with the
desired product 3aa in 46% yield based on GC
analysis (Table 1, entry 1). This preliminary results
inspired us for further optimization. Experimental
results showed that the solvents can dramatically
influence both conversion and selectivity of the
reaction. Replacement of CH3OH either with n-
heptane, toluene, MTBE, or CH2Cl2, both conversion
and selectivity were obviously improved (Table 1,
entries 2–5). Excitedly, nearly quantitative yield of the
product 3aa was obtained with THF as reaction
solvent under the same reaction conditions (Table 1,
Scheme 1. Transition-metal-free protocols for the synthesis of
arylchalcogenides from diorganyl dichalcogenides and arylbor-
onic acids.
entry 6). We also tested the reaction in 2-MeTHF,
which was considered as an environmentally benign
surrogate to THF.[24] Unfortunately, both the reaction
Adv. Synth. Catal. 2021, 363, 1–9
2
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
Table 1. Optimizing the reaction conditions.[a]
suitable for accomplishing this coupling reaction. Be-
sides of TCCA, other N-haloimides, such as NCS,
DCDMH, NBS and DBDMH, were also able to
perform the reaction. However, neither of them can be
competitive with TCCA (Table 1, entries 11–14 versus
entry 6). Furthermore, only marginal conversion was
observed when I2 and SO2Cl2 was employed as the
oxidant (Table 1, entries 15 and 16). Therefore, the
optimized reaction conditions for the cross-coupling
between diselenides and arylboronic acids are
0.33 equiv. of TCCA as the oxidant in THF under
ambient temperature for 4 h without any additive.
With the optimized reaction conditions in hand, we
then investigated the substrate scope of this TCCA-
promoted oxidative coupling protocol for the synthesis
of arylselenides. Firstly, the reaction activities of
various substituted phenyl boronic acids were eval-
uated by reaction with diphenyl diselenide (1a) and
the results were summarized in Table 2. Under the
optimized reaction conditions, a wide range of
electron-rich, electron-neutral and electron-deficient
aryl boronic acids 2b–2v could smoothly react with
1a to afford their corresponding arylselenides 3ab–
3av in good to excellent yields (75%–97%). It seemed
that both the electron property and the position of the
substituents attached on the phenyl ring had no obvious
effect on the reactivity. Lots of functional groups, such
as OCH3, SCH3, F, Cl, Br, CF3, CHO, COCH3,
COOCH3, CN and NO2, were tolerated under the
reaction conditions, thus providing the opportunity for
Entry Oxidant
[equiv.]
Solvent
Time Conv. Yield
[h]
[%][b]
[%][b]
1
TCCA
(0.33)
TCCA
(0.33)
TCCA
(0.33)
TCCA
0.33)
TCCA
(0.33)
TCCA
0.33)
TCCA
(0.33)
TCCA
(0.30)
TCCA
(0.33)
TCCA
(0.36)
NCS
CH3OH
n-Heptane
Toluene
MTBE
CH2Cl2
THF
4
68
46
2
4
4
4
4
4
4
4
3
4
8
4
8
4
4
4
84
61
3
94
88
4
95
91
5
98
96
6
>99
90
99(95)
79
7
2-MeTHF
THF
8
91
90
9
THF
98
97
10
11
12
13
14
15
16
THF
>99
88
99(94)
76
THF
(1.0)
DCDMH THF
(0.5)
NBS
(1.0)
DBDMH THF
(0.5)
98
96
THF
91
83
90
81
Table 2. Substrate scope of arylboronic acids for the synthesis
of arylselenides.[a,b]
I2
THF
<5
<5
trace
trace
(1.0)
SO2Cl2
(1.0)
THF
[a] Reaction conditions: diphenyl diselenide 1a (0.2 mmol,
0.5 equiv.), 4-methylphenyl boronic acid 2a (0.4 mmol,
1.0 equiv.), oxidant (x equiv. based on 2a) and solvent
(4 mL) under room temperature. TCCA=trichloroisocyanu-
ric acid, NBS=N-bromosuccinimide, NCS=N-chlorosucci-
nimide, DCDMH = 1,3-dichloro-5,5-dimethylhydantoin,
DBDMH=1,3-bromo-5,5-dimethylhydantoin.
[b] Conversions and yields were determined by GC analyses
with diphenyl as internal standard and the data in parentheses
were isolated yields.
rate and selectivity were much far inferior to those in
THF (Table 1, entry 7). The reaction did not go to
completion after either cutting down the amount of
TCCA or reducing the reaction time (Table 1, entries 8
and 9). Slightly increasing TCCA to 0.36 equivalent
did not improve the isolated yield (Table 1, entry 10).
Thus, stoichiometric amount of TCCA (0.33 equiv.) is
[a] Reaction conditions: diphenyl diselenide 1a (0.2 mmol),
(hetero)aryl boronic acid 2 (0.4 mmol), TCCA (0.133 mmol),
THF (4 mL) under room temperature for 4 h.
[b] Isolated yields.
[c] About 7% of 1-chloro-4-nitrobenzene was observed.
[d] About 10% of 1-chloronaphthalene was observed.
Adv. Synth. Catal. 2021, 363, 1–9
3
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
further derivatization. It was noted that high sterically Se coupling products 3db and 3dh can be obtained in
hindered 2,6-dimethylphenyl boronic acid (2v) can good yields (83% and 85%, respectively). Other than
also efficiently undergo this aryl-Se cross-coupling and diaryl diselenides, diheteroaryl diselenide (di(thiophen-
the corresponding product 3av was obtained up to 3-yl) diselenide 1e) and dialiphatic diselenides (dibutyl
82% yield. In addition, other than phenyl bronic acids, diselenide 1f, and dibenzyl diselenide 1g) were
naphthalen-1-yl boronic acid (2w) can be selenylated delightedly found to be capable as the organic
by 1a to generate the corresponding selenide 3aw in selenium sources for this coupling reaction. These can
78% yield under the identified reaction conditions. provide the efficient synthesis of heteroaryl-aryl and
Heteroaryl boronic acids, such as furan-3-yl boronic alkyl-aryl selenides. Under the same reaction condi-
acid (2x) and thiophen-3-yl boronic acid (2y), tions, 1e and 1f can smoothly reacted with 4-meth-
exhibited much lower activity on this transformation, ylphenyl bronic acid (2a) to give 3ea and 3fa in 78%
and their corresponding products 3ax and 3ay were and 85% yields, respectively. Whereas, for the reaction
only obtained in about 45% and 30% yields, of 1g, slightly higher dosage of TCCA (0.40 equiv.)
respectively.[25] In these two reactions, significant was needed to achieve good yield.
amounts of unknown by-products were observed. It
Considering the similarity of Se and Te, we would
should be noteworthy to point out that the reactions of like to extend this newly developed method to the
4-nitrophenyl boronic acid (2m) and naphthalen-1-yl synthesis of aryltelluride analogues (Table 4). As
boronic acid (2w) with 1a generated some chlorinated expected, with diphenyl ditelluride (4a) as organic
by-products, 1-chloro-4-nitrobenzene and 1-chloro- tellurium source and under the identified reaction
naphthalene, determined by GC-MS analyses.[26]
conditions, a number of functionalized phenyl boronic
Then, other diorganyl diselenides were explored in acids can smoothly undergo aryl-Te cross-coupling
this coupling reaction. The results were listed in reactions to afford the desired aryltelluride products
Table 3. Both electron-donating group (CH3, 1b) and 5ab, 5ad–5ag and 5aj in good to excellent yields
electron-withdrawing group (Cl, 1c) substituted di- (80%–91%). Many functionalized groups, such as
phenyl diselenides exhibited similar reactivity to model OMe, F, Cl, Br and COCH3, can be tolerated. Different
diselenide substrate 1a. After reaction with different to the aryl-Se formation reactions, the electron prop-
kinds of phenyl boronic acids, a variety of arylsele- erty of the substituents attached on the phenyl ring
nides, such as 3ba, 3ca, 3cb and 3cf, were obtained affected the outcome of the reactions somewhat. In
in good to excellent yields (82%-92%). Sterically general, the electron-deficient phenyl boronic acids
hindered dimesityl diselenide (1d) showed less reac-
tive under room temperature. However, such slow
reactions can be compensated by slightly increasing
Table 4. Synthesis of aryltellurides from aryl boronic acids and
°
reaction temperature to 40 C, their corresponding aryl-
diorganyl distellurides. [a,b]
Table 3. Substrate scope of diorganyl diselenides for the
synthesis of arylselenides.[a,b]
[a] Reaction conditions: diorganyl diselenides 1 (0.2 mmol), aryl
boronic acids 2 (0.4 mmol), TCCA (0.133 mmol), THF
(4 mL) under room temperature for 4 h.
[a] Reaction conditions: diorganyl ditellurides 4 (0.2 mmol),
(hetero)aryl boronic acid 2 (0.4 mmol), TCCA (0.133 mmol),
THF (4 mL) under room temperature for 4 h.
[b] Isolated yields.
[b] Isolated yields.
[c]
°
Reacted at 40 C.
[d] TCCA (0.160 mmol).
Adv. Synth. Catal. 2021, 363, 1–9
4
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
provided slightly lower yields than their electron-rich Meanwhile, the oxidation system was not suitable for
analogues. Interestingly, heteroaryl boronic acids, phenyl boronic acid pinacol ester (8). In this case, the
thiophen-3-yl boronic acid (2x) and furan-3-yl boronic starting materials were inert even elongating the
acid (2y), showed good reactivity toward 4a, and reaction to 12 h.
corresponding aryltellurides (5ax and 5ay) were
Encouraged by the above presented results and
obtained in 78% and 63% yields, respectively. Fur- further demonstrating the utility of the newly devel-
thermore, with di(4-methylphenyl) ditelluride (4b), oped method, four reactions on a gram scale (5 mmol
di(4-fluorophenyl) ditelluride (4c) and di(4-chloro- of organoboronic acids) were carried out. Delightfully,
phenyl) ditelluride (4d) as other aryl tellurium sources no obvious deviation in yields was observed
and dibutyl ditelluride (4e) as alkyl tellurium source, (Scheme 3).[28] Moreover, after completion of the
diaryl tellurides (5ba, 5cl and 5dl) and alkyl-aryl reactions, THF was switched with MTBE, the oxida-
tellurides (5ea, 5eb and 5ef) were obtained in 67– tion by-product isocyanuric acid was quantitatively
91% yields. Nevertheless, the protocol was incapable recovered as white precipitate. In fact, the recycling of
of transferring heteroaromatic ditellurides, such as isocyanuric acid to TCCA is a known process in
(di(thiophen-3-yl) ditelluride and di(pyridin-3-yl) ditel- industry. Thus, we are confident that this oxidation
luride. Both reactions of these two ditellurides with 4- protocol is a high atom-efficient and eco-friendly
methylphenyl boronic acid predominately produced 4- process.
methylphenyl chloride instead of coupling products.[26]
The delightful results of this new protocol for
It should be noted that most of aryltellurides were synthesizing arylselenides and aryltellurides stimulated
unstable in air and easy to be oxidized during the us to explore the potential reaction mechanism. It has
work-up procedure, which was also previously men- been reported that diorganyl dichalcogenides can be
tioned by Wang and co-workers.[10f] Hopefully, this cleaved by N-haloimides to form corresponding orga-
stability issue can be solved by adding a little amount nochalcogeno halides and N-organochalcogeno-substi-
of sodium hydrosulfite to the reaction mixture before tuted imide derivative.[29] Then, we tested coupling
work-up. With this slight modification, the desired reactions of 4-methylphenyl boronic acid (2a) with
aryltellurides can be smoothly isolated in satisfied phenyl selenium chloride (9) and N,N,N-triphenylsele-
purity. We also attempted to extend this method for nylisocyanuric acid (10) under the identified reaction
arylsulfides synthesis by reacting diorganyl disulfides conditions.[30] These two reactions afforded 3aa only
with aryl boronic acids. Unfortunately, no aryl-S in 30% and 42% yields, respectively. While similar
coupling products was formed under identified reaction yields (95% and 93%) were obtained with the
conditions,[27] which was ascribed to the much higher promotion of TCCA (Scheme 4a and 4b). These
SÀ S bond dissociation energy of disulfides than those experimental results can rule out either organoselenium
of SeÀ Se and TeÀ Te bonds.
chlorides or N-organoseleno-substituted imide deriva-
Next, we tested the reaction activity of phenyl tives as the actual active intermediate in this protocol.
boronic acid derivatives for this transformation The possibility of radical path was also evaluated by
(Scheme 2). The experimental results showed that aryl performing the standard reaction in the presence of
trifluoroborates and aryl trihydroxyborate salts were 1.0 equiv. of 2,2,6,6-tetramethylpiperidine-1-oxyl
also efficient. By reacting diphenyl diselenide (1a) (TEMPO) as radical inhibitor. High yield of 3aa
with potassium phenyl trifluoroborate (6) or sodium strongly suggested that no radical intermediate was
phenyl trihydroxyborate (7) under the identified reac- involved in this oxidative cross-coupling process
tion conditions, the desired product 3ad was obtained (Scheme 4c).
in comparable 90% and 91% yields, respectively.
For more detailed reaction mechanism, the model
reaction was further studied using 77Se NMR spectro-
scopy and the experimental results are shown in
Scheme 5. A mixture of TCCA and diphenyl disele-
Scheme 2. Evaluation of reaction activity of phenyl boronic
acid derivatives.
Scheme 3. Gram-scale reactions.
Adv. Synth. Catal. 2021, 363, 1–9
5
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
Scheme 6. Plausible reaction pathway.
Scheme 4. Control experiments.
On the basis of our experimental results and the
previous reported works,[18,32] we proposed a plausible
reaction pathway for our developed protocol
(Scheme 6). Firstly, diorganyl dichalcogenides (1 or 4)
were oxidiaed by TCCA to generate cationic organic
chalcogenium complexs 11 with an imide counterion
and Cl2. Then, the intermediates 11 underwent electro-
philc ipso-substitution reaction with arylboronic acids
to provide the desired chalcogenated products (3 or 5).
In the ipso-substitution reaction step, the imide
counterion played an important role in the activation of
arylboronic acids by coordination with B atom. We
attempted to demonstrate this pathway by HRMS. But
none of the intermediates (11 and 12) were detected.
More detailed mechanism is carrying out in our Lab.
Scheme 5. 77Se NMR (THF-d8) spectra of the proposed inter-
mediate.
Conclusion
In summary, we have successfully developed a new
transition-metal-free protocol for the synthesis of
arylchalcogenides (selenides and tellurides). With
nide (1a) with a molar ratio of 0.33 : 1 in THF-d8 gave TCCA as the chemical oxidant, a wide range of
a pair of new signals at 1044.14 ppm and 978.17 ppm unsymmetrical (hetero)aryl-aryl, alkyl-aryl selenides
(Scheme 5a). After adding 2.0 equiv. (based on 1a) of and tellurides can be synthesized in good to excellent
4-methyl phenylboronic acid (2a) to this mixture, the yields under ambient temperature from diorganyl
signal at 978.17 ppm was disappeared along with the dichalcogenides and (hetero)aryl boronic acids. Three
emerging of a new signal at 405.47 ppm (Scheme 5b). reaction reagents employed in this method was
By comparison with authentic reference substances, we stoichiometric and no other additives was required. In
identified the signals at 1044.14, 461.00, and addition, the reaction by-product isocyanuric acid can
405.47 ppm as to be phenylselenium chloride (9), be quantitatively recovered to regenerate TCCA for
diphenyl diselenide (1a) and 4-methylphenyl phenyl reuse. Therefore, the newly developed method pro-
selenide (3aa), respectively. Moreover, we found that vided a robust, economic, eco-friendly, easy-to-operate
77
the Se chemical shift value of N,N,N-triphenylselenyl alternative for arylselenides and aryltellurides syn-
isocyanuric acid (10) was 1191.72 ppm. These results thesis.
indicated the signal at 978.17 ppm was a new selenium
species and it was the actual active intermediate in this
Experimental Section
aryl-chalcogen bond formation reaction. Inspired by
Kumar’s work,[31] we speculated that this selenium General procedure for the synthesis of arylselenides
species might be phenylselenium cation (PhSe+), and aryltellurides
which was generated from oxidation of diphenyl
To
a 15 mL of Young tube, diorganyl dichalcogenide
diselenide by TCCA. In additon, we found that the
reaction gradually released Cl2 gas by KI-starch test
(See supporting inforamtion).
(0.2 mmol), arylboronic acid (0.4 mmol) and THF (4.0 mL)
were successively added. The mixture was stirred for about
Adv. Synth. Catal. 2021, 363, 1–9
6
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
5 min until dissolution, and then TCCA (0.133 mmol) was
portion-wise added over a period of 1–2 min. The resulted
reaction mixture was stirred at ambient reaction temperature
skaya, V. P. Ananikov, Chem. Rev. 2011, 111, 1596; f) G.
Mugesh, H. B. Singh, Acc. Chem. Res. 2002, 35, 226.
[8] D. G. Hall, Boronic Acids-Preparation and Applications
in Organic Synthesis, Medicine and Materials, Wiley-
VCH, Weinheim, 2011.
[9] A. Ivanova, P. Arsenyan, Coord. Chem. Rev. 2018, 370,
55.
[10] For reviews, see: a) S. Koguchi, Y. Shibuya, Y. Igarashi,
H. Takemura, Synlett 2019, 30, 99; b) S. Saba, G. V.
Botteselle, M. Godoi, T. E. Allievi Frizon, F. Z. Galetto,
J. Rafique, A. L. Braga, Molecules 2017, 22, 1367; c) A.
Kumar, S. Kumar, Tetrahedron 2014, 70, 1763; d) V. G.
Ricordi, C. S. Freitas, G. Perin, E. J. Lenardao, R. G.
Jacob, L. Savegnago, D. Alves, Green Chem. 2012, 14,
1030; e) N. Taniguchi, J. Org. Chem. 2007, 72, 1241;
f) L. Wang, M. Wang, F. P. Huang, Synlett 2005, 16,
2007.
°
(25–30 C) for 4 h. After the reaction was finished, the crude
mixture was condensed, followed by addition of MTBE (5 mL)
to precipitate the oxidation by-product isocyanuric acid. This
precipitation was recovered by centrifugation, and the mother
liquor was decanted and concentrated under vacuum. Finally,
the residual was purified by flash chromatography on silica
with a mixture of petroleum ether/ethyl acetate as the eluent to
afford the desired products. For the synthesis of aryltellurides,
0.1 g of sodium hydrosulfite was preferably added before work-
up.
Acknowledgements
This work was supported by the National Natural Science
Foundations of China (21972125) and “Zhejiang Key Labo-
ratory of Green Pesticides and Cleaner Production Technology
of Zhejiang Province”. We also thank Porf. Wanli Chen (ZJUT)
for technical assistance in the NMR experiments.
[11] M. Wang, K. Ren, L. Wang, Adv. Synth. Catal. 2009,
351, 1586.
[12] K. Ren, M. Wang, L. Wang, Org. Biomol. Chem. 2009,
7, 4858.
[13] a) B. Goldani, M. do Sacramento, E. J. Lenardao, R. F.
Schumacher, T. Barcellos, D. Alves, New J. Chem. 2018,
42, 15603; b) B. Goldani, V. G. Ricordi, N. Seus, E. J.
Lenardao, R. F. Schumacher, D. Alves, J. Org. Chem.
2016, 81, 11472.
[14] a) C.-L. Sun, Z.-J. Shi, Chem. Rev. 2014, 114, 9219;
b) C. E. Garrett, K. Prasad, Adv. Synth. Catal. 2004, 346,
889.
[15] a) H. Zhao, Y. Jiang, Q. Chen, M. Cai, New J. Chem.
2015, 39, 2106; b) B. Mohan, C. Yoon, S. Jang, K. H.
Park, ChemCatChem 2015, 7, 405; c) S. Roy, T.
Chatterjee, B. Banerjee, N. Salam, A. Bhaumik, S. M.
Islam, RSC Adv. 2014, 4, 46075; d) D. Kundu, N.
Mukherjee, B. C. Ranu, RSC Adv. 2013, 3, 117; e) D.
Alves, C. G. Santos, M. W. Paixao, L. C. Soares, D.
de Souza, O. E. D. Rodrigues, A. L. Braga, Tetrahedron
Lett. 2009, 50, 6635.
References
[1] a) E. R. T. Tiekink, Dalton Trans. 2012, 41, 6390;
b) C. W. Nogueira, J. B. T. Rocha, Arch. Toxicol. 2011,
85, 1313; c) C. W. Nogueira, G. Zeni, J. B. T. Rocha,
Chem. Rev. 2004, 104, 6255; d) G. Mugesh, W. W.
du Mont, H. Sies, Chem. Rev. 2001, 101, 2125.
[2] a) L. X. Shao, Y. M. Li, J. M. Lu, X. F. Jiang, Org.
Chem. Front. 2019, 6, 2999; b) F. V. Singh, T. Wirth,
Catal. Sci. Technol. 2019, 9, 1073; c) A. L. Braga, D. S.
Ludtke, F. Vargas, R. C. Braga, Synlett 2006, 17, 1453;
d) T. Wirth, Angew. Chem. Int. Ed. 2000, 39, 3740.
[3] a) P. Oswal, A. Arora, S. Singh, D. Nautiyal, S. Kumar,
G. K. Rao, A. Kumar, Dalton Trans. 2020, 49, 12503;
b) A. Kumar, G. K. Rao, F. Saleem, A. K. Singh, Dalton
Trans. 2012, 41, 11949; c) M. Godoi, M. W. Paixao,
A. L. Braga, Dalton Trans. 2011, 40, 11347.
[16] S. Saba, J. Rafique, A. L. Braga, Adv. Synth. Catal. 2015,
357, 1446.
[17] G. Perin, L. F. B. Duarte, J. S. S. Neto, M. S. Silva, D.
Alves, Synlett 2018, 29, 1479.
[4] S. T. Manjare, Y. Kim, D. G. Churchill, Acc. Chem. Res.
2014, 47, 2985.
[5] a) E. J. Lenardao, J. D. Feijo, S. Thurow, G. Perin, R. G.
Jacob, C. C. Silveira, Tetrahedron Lett. 2009, 50, 5215;
b) E. J. Lenardao, E. L. Borges, S. R. Mendes, G. Perin,
R. G. Jacob, Tetrahedron Lett. 2008, 49, 1919; c) E. J.
Lenardao, S. R. Mendes, P. C. Ferreira, G. Perin, C. C.
Silveira, R. G. Jacob, Tetrahedron Lett. 2006, 47, 7439.
[6] Q. L. Li, Y. Y. Zhang, Z. J. Chen, X. Q. Pan, Z. B.
Zhang, J. Zhu, X. L. Zhu, Org. Chem. Front. 2020, 7,
2815.
[7] a) W. B. Ma, N. Kaplaneris, X. Y. Fang, L. H. Gu, R. H.
Mei, L. Ackermann, Org. Chem. Front. 2020, 7, 1022;
b) D. E. Jose, U. S. Kanchana, T. V. Mathew, G. Anilku-
mar, Curr. Org. Chem. 2020, 24, 1230; c) D. S. Rampon,
E. Q. Luz, D. B. Lima, R. A. Balaguez, P. H. Schneider,
D. Alves, Dalton Trans. 2019, 48, 9851; d) G. Perin, D.
Alves, R. G. Jacob, A. M. Barcellos, L. K. Soares, E. J.
Lenardao, ChemistrySelect 2016, 1, 205; e) I. P. Belet-
[18] R. An, L. H. Liao, X. Liu, S. Q. Song, X. D. Zhao, Org.
Chem. Front. 2018, 5, 3557.
[19] For reviews, see: a) S. Gaspa, M. Carraro, L. Pisano, A.
Porcheddu, L. De Luca, Eur. J. Org. Chem. 2019, 2019,
3544; b) G. F. Mendonca, M. C. S. de Mattos, Curr. Org.
Chem. 2013, 10, 820; c) U. Tilstam, H. Weinmann, Org.
Process Res. Dev. 2002, 6, 384.
[20] S. D. F. Tozetti, L. S. de Almeida, P. M. Esteves,
M. C. S. de Mattos, J. Braz. Chem. Soc. 2007, 18, 675.
[21] C. C. Silveira, S. R. Mendes, L. Wolf, G. M. Martins, L.
von Muhlen, Tetrahedron 2012, 68, 10464.
[22] a) D. Bornemann, C. R. Pitts, C. J. Ziegler, E. Pietrasiak,
N. Trapp, S. Kueng, N. Santschi, A. Togni, Angew.
Chem. Int. Ed. 2019, 58, 12604; b) C. R. Pitts, D.
Bornemann, P. Liebing, N. Santschi, A. Togni, Angew.
Chem. Int. Ed. 2019, 58, 1950.
Adv. Synth. Catal. 2021, 363, 1–9
7
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
asc.wiley-vch.de
[23] J. S. S. Neto, R. Kruger, R. A. Balaguez, M. G. Fronza,
T. V. Acunha, R. S. Oliboni, L. Savegnago, B. A.
Iglesias, D. Alves, New J. Chem. 2020, 44, 2768.
[24] V. Pace, P. Hoyos, L. Castoldi, P. D. de Maria, A. R.
Alcantara, ChemSusChem 2012, 5, 1369.
Park, S. B. Jang, K.-T. Ha, Sci. Rep. 2019, 9, 1), and 5ae
is a building block for the construction of novel
phosphorescence materials (L. Xu, G. Li, T. Xu, W.
Zhang, S. Zhang, S. Yin, Z. An, G. He, Chem. Commun.
2018, 54, 9226).
[25] We could not isolate 3ay in satisfied purity.
[29] a) T. Hori, K. B. Sharpless, J. Org. Chem. 1979, 44,
4208; b) D. Huang, J. Chen, W. Dan, J. Ding, M. Liu, H.
Wu, Adv. Synth. Catal. 2012, 354, 2123.
[30] Phenyl selenium chloride (9) is commercially available,
and N,N,N-triphenylselenylisocyanuric acid (10) is syn-
thesized according to literature procedure, see: B.
Movassagh, A. Takallou, Synlett 2015, 26, 2247.
[26] a) G. A. Molander, L. N. Cavalcanti, J. Org. Chem.
2011, 76, 7195; b) R. H. Szumigala, P. N. Devine, D. R.
Gauthier, R. P. Volante, J. Org. Chem. 2004, 69, 566.
[27] Silveira and co-workers reported that MgO can promote
the TCCA-mediated oxdative coupling of diaryl disele-
nides and indoles to produce 3-sulfenyl or 2,3-disufenyl
substituted indoles (see reference 21). Nevertheless, we [31] C. D. Prasad, S. J. Balkrishna, A. Kumar, B. S. Bhakuni,
still could not obtain arylsulfides from diaryl diselenides,
arylboronic acids and TCCA in the presence of 1.0 equiv.
of MgO.
K. Shrimali, S. Biswas, .S. Kumar, J. Org. Chem. 2013,
78, 1434.
[32] C. Zhu, J. R. Falck, Adv. Synth. Catal. 2014, 356, 2395.
[28] 3ah is a highly active lactate dehydrogenase inhibitor
(E.-Y. Kim, T.-W. Chung, C. W. Han, S. Y. Park, K. H.
Adv. Synth. Catal. 2021, 363, 1–9
8
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

RESEARCH ARTICLE
Trichloroisocyanuric Acid-Promoted Synthesis of Arylsele-
nides and Aryltellurides from Diorganyl Dichalcogenides and
Arylboronic Acids at Ambient Temperature
Adv. Synth. Catal. 2021, 363, 1–9
N. Sun*, K. Zheng, P. Sun, Y. Chen, L. Jin, B. Hu, Z. Shen,
X. Hu*