Catalytic Asymmetric Disulfuration by a Chiral Bulky Three‐Component Lewis Acid‐Base

Abstract A three‐component Lewis acid–base (Lewis trio) involving a bulky chiral primary amine, B(C 6 F 5 ) 3 and a bulky tertiary amine has been developed as an effective enamine catalyst for enantioselective disulfuration reactions. The bulky tertiary amine was found to activate a bulky primary–tertiary diamine–borane Lewis pair for enamine catalysis via frustrated interaction. The resulted chiral bulky Lewis trio (BLT) allows for the construction of chiral disulfides via direct disulfuration with β‐ketocarbonyls or α‐branched aldehydes in a practical and highly stereocontrolled manner.