A range of primary allylic amines were resolved with selectivity factors of up to 491 through [Pd(allyl)Cl]2/(S)-BINAP-catalyzed and mesitylsulfonyl hydrazide-accelerated asymmetric allylic alkylation of malononitriles involving enantioselective C–N bond cleavage under aerobic conditions. Moreover, the reaction proved useful for the asymmetric synthesis of α-branched allyl-substituted malononitriles with high enantiopurity.
