Asymmetric Retro-Claisen Reaction by Synergistic Chiral Primary Amine/Palladium Catalysis

We described herein a chiral primary amine/palladium catalyzed asymmetric retro-Claisen reaction of beta-diketones with salicylic carbonates. A series of chiral alpha-alkylated ketones and macrolides were obtained with good yields and excellent enantioselectivities upon a sequence of decarboxylative benzylation, retro-Claisen cleavage, and enamine protonation. This strategy features broad substrate scope, mild conditions, as well as high atom economy with salicylic carbonates as the o-quinone methide precursors.