F₁₀BINOL-derived chiral phosphoric acid-catalyzed enantioselective carbonyl-ene reaction: theoretical elucidation of stereochemical outcomes.

ABSTRACT: An F₁₀BINOL-derived chiral phosphoric acid was shown to be an effective catalyst for an enantioselective carbonyl-ene reaction of 1,1-disubstituted olefins with ethyl glyoxylate as the common enophile. The perfluoro-binaphthyl skeleton is beneficial not only for adopting high catalytic activity but also for creating an effective chiral environment for enantioselective transformations. Indeed, the reaction afforded enantio-enriched homoallylic alcohols in high yields with high enantioselectivities. Theoretical studies identified that the multi-point C-H···O hydrogen bonds and the π interactions between the substrates and the 6-methoxy-2-naphthyl substituents at the 3,3'-positions of the F₁₀BINOL skeleton play a crucial role in determining the stereochemical outcomes. The significance of the perfluoro-binaphthyl skeleton in achieving the high enantioselectivity was also evaluated through a structural analysis of the catalysts.

SUBMITTER: Kikuchi J 

PROVIDER: S-EPMC6354837 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature