Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol

[Image: see text] 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–π interactions between the nucleophile, electrophile, and catalyst to induce selectivity.