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Comprehensive Summary: Lewis 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. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Lewis 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. [ABSTRACT FROM AUTHOR]

An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed for the first time. This was achieved by using a new Lewis base catalyst and a new ortho‐trifluoromethyl‐substituted sulfenylating reagent. Using the substrates with low rotational energy barrier, the transformation proceeded through a dynamic kinetic resolution, and the high rotational energy barrier of the substrates allowed the reaction to undergo a kinetic resolution process. Meanwhile, this transformation was compatible with a desymmetrization process when the symmetric substrates were used. Various planar‐chiral sulfur‐containing cyclophanes were readily obtained in moderate to excellent yields with moderate to excellent enantioselectivities (up to 97 % yield and 95 % ee). This approach was used to synthesize pharmaceutically relevant planar‐chiral sulfur‐containing molecules. Density functional theory calculations showed that π‐π interactions between the sulfenyl group and the aromatic ring in the substrate play a crucial role in enantioinduction in this sulfenylation reaction. [ABSTRACT FROM AUTHOR]