Catalytic Asymmetric Hydroperoxidation of α,β‐Unsaturated Ketones: An Approach to Enantiopure Peroxyhemiketals, Epoxides, and Aldols

Efficient, selective: The primary amine salt 1 derived from quinine efficiently catalyzes the highly enantioselective hydroperoxidation of α,β-unsaturated ketones furnishing stable and isolable cyclic peroxyhemiketals in enantiopure form. The versatility of the peroxyhemiketals was demonstrated with the syntheses of aldols and epoxides from α,β-unsaturated ketones and hydrogen peroxide (see scheme).