Synergistic Cu-amine catalysis for the enantioselective synthesis of chiral cyclohexenonesElectronic supplementary information (ESI) available: General procedures, optimization tables, and experimental and spectroscopic data for all compounds. See DOI: 10.1039/c5cc02987b

An unprecedented utilization of 1,3-acetonedicarboxylic acid as a 1,3-bis-pro-nucleophile and a reactive acetone surrogate in enantioselective catalysis has been reported. By synergistically activating the ketodiacid by copper catalysis and an α,β-unsaturated aldehyde by amine catalysis, an efficient domino di-decarboxylative Michael/aldol/dehydration sequence takes place leading to valuable chiral cyclohexenones in one single operation in 94 to 99% ee. An unprecedented utilization of 1,3-acetonedicarboxylic acid as a 1,3-bis-pro-nucleophile and a reactive acetone surrogate in enantioselective catalysis has been reported.