Transition-Metal-Free Synthesis of Unsymmetrical Diaryl Chalcogenides from Arenes and Diaryl Dichalcogenides

A transition-metal-free synthetic method has been developed for the synthesis of unsymmetrical diaryl chalcogenides (S, Se, and Te) from diaryl dichalcogenides and arenes under oxidative conditions by using potassium persulfate at room temperature. Variously substituted arenes such as anisole, thioa...

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Bibliographic Details
Published in:Journal of organic chemistry 2013-02, Vol.78 (4), p.1434-1443
Main Authors: Prasad, Ch Durga, Balkrishna, Shah Jaimin, Kumar, Amit, Bhakuni, Bhagat Singh, Shrimali, Kaustubh, Biswas, Soumava, Kumar, Sangit
Format: Article
Language:English
Subjects:
Aniline Compounds - chemistry
Catalysis
Chalcogens - chemical synthesis
Chalcogens - chemistry
Magnetic Resonance Spectroscopy
Molecular Structure
Transition Elements - chemistry
Trifluoroacetic Acid - chemistry
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Summary:A transition-metal-free synthetic method has been developed for the synthesis of unsymmetrical diaryl chalcogenides (S, Se, and Te) from diaryl dichalcogenides and arenes under oxidative conditions by using potassium persulfate at room temperature. Variously substituted arenes such as anisole, thioanisole, diphenyl ether, phenol, naphthol, di- and trimethoxy benzenes, xylene, mesitylene, N,N-dimethylaniline, bromine-substituted arenes, naphthalene, and diaryl dichalcogenides underwent carbon–chalcogen bond-forming reaction to give unsymmetrical diaryl chalcogenides in trifluoroacetic acid. To understand the mechanistic part of the reaction, a detailed in situ characterization of the intermediates has been carried out by 77Se NMR spectroscopy by using diphenyl diselenide as the substrate. 77Se NMR study suggests that electrophilic species ArE+ is generated by the reaction of diaryl dichalcogenide with persulfate in trifluoroacetic acid. The electrophilic attack of arylchalcogenium ion on the arene may be responsible for the formation of the aryl–chalcogen bond.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo302480j