Asymmetric organocatalytic desymmetrization of 4,4-disubstituted cyclohexadienones at high pressure: a new powerful strategy for the synthesis of highly congested chiral cyclohexenones.

A highly diastereoselective and enantioselective method for the asymmetric desymmetrization of 4,4-disubstituted cyclohexadienones using the Michael addition reaction of malonates under catalysis with the primary amine-thiourea conjugate catalyst and PPY at high pressure was developed.