Search

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 enantioselective sulfenylation/semipinacol rearrangement of 1,1‐disubstituted and trisubstituted allylic alcohols was accomplished with a chiral Lewis base and a chiral Brønsted acid as cocatalysts, generating various β‐arylthio ketones bearing an all‐carbon quaternary center in moderate to excellent yields and excellent enantioselectivities. These chiral arylthio ketone products are common intermediates with many applications, for example, in the design of new chiral catalysts/ligands and the total synthesis of natural products. Computational studies (DFT calculations) were carried out to explain the enantioselectivity and the role of the chiral Brønsted acid. Additionally, the synthetic utility of this method was exemplified by an enantioselective total synthesis of (−)‐herbertene and a one‐pot synthesis of a chiral sulfoxide and sulfone. [ABSTRACT FROM AUTHOR]