Communications
doi.org/10.1002/ejoc.202001465
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Synthesis of 2-Substituted Benzothio(seleno)phenes and
Indoles via Ag-Catalyzed Cyclization/Demethylation of 2-
Alkynylthio(seleno)anisoles and 2-Alkynyldimethylanilines
Tao Cai,[a] Chengjie Feng,[a] Fangqi Shen,[a] Kejun Bian,[a] Chunlei Wu,[a] Runpu Shen,*[a] and
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An Ag-catalyzed cyclization/demethylation of 2-alkynylthio
(seleno)anisoles and 2-alkynyldimethylanilines is described and
applied for the construction of valuable benzothio(seleno)
phenes as well as indoles. Various 2-substituted benzothio
(seleno)phenes and indoles were obtained in good to excellent
yields under mild reaction conditions with low catalyst loading.
An application of this new method is also exemplified with a
concise synthesis of a bioactive molecule precursor. Further-
more, a conceivable reaction mechanism is proposed with
supports from isotope-exchange experiments.
Figure 1. Representative drugs and biologically active molecules with
benzothio(seleno)phene and indole motif.
(Hg(OAc)2, CuCl2, CuBr2, etc.) has been proven to be one of the
Introduction
most efficient and valuable ways[6a–k,8a–e] (Scheme 1). For exam-
ple, by employing this methodology, Flynn’s,[6a] Larock’s,[6b–e,8a–e]
Sanz’s,[6i] Wu’s,[6f] Balova’s[8i] and Kesharwani’s[6j,k] groups re-
ported a series of 2,3-disubstituted benzothio(seleno)phenes or
indoles, respectively. Ingleson and co-workers have described
the preparation of C3-borylated benzofurans and benzothio-
phenes by using BCl3 as an electrophilic partner.[9] Muchalski
and co-workers disclosed the synthesis of 2-substituted benzo-
thiophenes from 2-alkynyl thioanisoles by using 1 mol%
loading of Au(IPr)OH as a catalyst and 100 mol% AcOH as a
protodeauration additive.[10] Generally, these electrophilic cycli-
zation reactions are very efficient and proceed under very mild
reaction conditions with good functional group tolerance.
However, in some cases, these protocols still suffer some
limitations, such as the use of corrosive halogens or toxic
transition-metal salts, the need for a more-than-stoichiometric
amount of electrophilic reagents, or the application of
expensive catalysts. For these reasons, the development of
alternative approaches based on less toxic and cheaper
catalysts, such as silver species, will be highly desirable for
synthetic organic chemists.
Benzothio(seleno)phenes and indoles are important heterocy-
clic scaffolds that have been widely found in many pharmaceut-
icals, natural products, and material science.[1,2] For example,
Zileuton is a market-available drug, which has been widely used
for the treatment of asthma.[3] 2-Butyl-1-(4-carboxybenzyl)-5-[2-
carboxy-3-(benzo[b]selenophen-1-yl)prop-1-enyl]-1H-imidazole
is proved to be an excellent AT1 receptor antagonist.[4]
Ondansetron has been widely used for the suppression of
nausea and vomit caused by cancer chemotherapy and
radiotherapy[5] (Figure 1). Therefore, continuous efforts have
been directed towards the development of efficient methods
for constructing these heterocyclic scaffolds in organic synthesis
and medicinal chemistry.
In the past few decades, a variety of concise and robust
synthetic methods have been established for the synthesis of
substituted benzothio(seleno)phenes[6,7] and indoles.[8] Among
them, the intramolecular 5-endo-dig electrophilic cyclization
and demethylation of 2-alkynylthio(seleno)anisoles or 2-
alkynyldimethylanilines in the presence of electrophilic reagents
(I2, Br2, NBS, PhSeCl, ICl, etc.), as well as transition-metal catalysts
As part of our ongoing interests in the study of new
advantageous silver-catalyzed approaches for the synthesis of
N/S-containing heterocycles starting from 2-alkynylthioanisoles
[a] Dr. T. Cai, C. Feng, F. Shen, K. Bian, C. Wu, Prof. R. Shen
Department College of Chemistry and Chemical Engineering
Shaoxing University,
Shaoxing 312000, P. R. China
E-mail: srunpu@usx.edu.cn
[b] Dr. Y. Gao
Key Laboratory of Coal to Ethylene Glycol and Its Related Technology
Fujian Institute of Research on the Structure of Matter, Chinese Academy of
Sciences,
Fuzhou 350002, P. R. China
E-mail: gyz@fjirsm.ac.cn
Supporting information for this article is available on the WWW under
Scheme 1. Electrophilic cyclization of 2-alkynylthio(seleno)anisoles.
Eur. J. Org. Chem. 2021, 653–656
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