Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol

Abstract

Current models for oxazaborolidine-catalyzed transition-state structures are determined by C-H···O-B and C-H···O=S formyl hydrogen bonding between the electrophile and catalyst. However, selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannot be fully rationalized using these models. Combined density functional theory and noncovalent interaction analyses reveal a new reaction model relying on C-H···O, C-H···π, and π-πinteractions between the nucleophile, electrophile, and catalyst to induce selectivity.