The enantioselective Michael addition reaction of α‐substituted cyclic ketones with acrylates was efficiently promoted by a primary amine chiral catalyst under high‐pressure conditions (1.0 GPa) in tetrahydrofuran. This method was highly successful for the construction of an all‐carbon‐substituted quaternary‐carbon stereogenic center at the α‐position of cyclic ketones in high enantiomeric excess, and could be conveniently applied to the formal synthesis of (+)‐aspidospermidine.

High Pressure Organic Chemistry. Part 40. Enantioselective Synthesis of Quaternary Carbon Stereogenic Centers Through the Primary Amine-Catalyzed Michael Addition Reaction of -Substituted Cyclic Ketones at High Pressure. -Compounds bearing a quaternary carbon stereogenic center at the -position of cyclic ketones are obtained by an efficient new method involving the enantioselective Michael addition of cyclic ketones with acrylates using simple chiral 1-phenylethylamine as catalyst under high pressure. -(HORINOUCHI, R.; KAMEI, K.; WATANABE, R.; HIEDA, N.; TATSUMI, N.; NAKANO, K.; ICHIKAWA, Y.; KOTSUKI*, H.; Eur.