Abstract

Comprehensive SummaryLewis base catalyzed and Brønsted acid controlled chemodivergent electrophilic selenofunctionalizations of alkynes were developed for the first time. Various selenium‐containing tetrasubstituted alkenes were readily obtained in moderate to excellent yields with complete E/Z selectivities. As the substrates were 1‐ethynyl naphthol derivatives, linear selenium‐containing tetrasubstituted alkenes were produced via intermolecular oxygen nucleophilic attack in the absence of acid additive; in contrast, cyclic selenium‐containing tetrasubstituted alkenes were generated through intramolecular carbon nucleophilic capture with the addition of Brønsted acid.

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