Double Asymmetric Hydrogenation of Linear β,β-Disubstituted α,β-Unsaturated Ketones into γ-Substituted Secondary Alcohols using a Dual Catalytic System.

Double asymmetric hydrogenation of linear β,β-disubstituted α,β-unsaturated ketones catalyzed by the DM-SEGPHOS/DMAPEN/Ru complex with t-C H OK afforded the γ-substituted secondary alcohols in high diastereo- and enantioselectivities. Some mechanistic experiments suggested that two different reactive species, type (I) and (II), were reversibly formed in this catalytic system: Type (I) with the diamine ligand DMAPEN enantioselectively hydrogenated the enones into the chiral allylic alcohols, and type (II) without the diamine ligand diastereoselectively hydrogenated the allylic alcohols into the γ-substituted secondary alcohols. This dual catalysis protocol was successfully applied to the reaction of a variety of aliphatic- and aromatic-substituted enone substrates.