Asymmetric Catalytic Oxa- and Aza-Michael Addition by Organic Catalyst

We have developed the first highly enantioselective peroxidation reaction of alpha,beta-unsaturated ketones by employing an easy accessible bifunctional organic catalyst derived from cinchona alkaloid which not only induced enantioselectivity but also converted a well-established epoxidation pathway into a peroxidation pathway. This new developed asymmetric peroxidation could not only provide the beta-hydroxyl ketone which has the wide application in the polyketide type of natural products systhesis, but also afford the asymmetric chiral peroxide which is expected to open new possibilities in the asymmetric synthesis of the biological interesting chiral peroxides. Furthermore, with the same catalyst and regents, a highly asymmetric epoxidation of alpha,beta-unsaturated ketones could also be achieved with higher temperature.;The first highly enantioselective peroxidation of both aromatic and aliphatic alpha,beta-unsaturated nitroalkene was developed. Employing the easily accessible acid-base bifunctional catalysts based on the cinchona alkaloids, the novel asymmetric peroxidation has the great potential for the asymmetric synthesis of alpha-peroxyl carbonyl chiral compounds.;Bifunctional cinchona alkaloids were found to promote the first highly enantioselective organocatalytic aza-Michael reactions with alpha,beta-unsaturated ketones. In addition to utilizing practical catalysts, readily accessible substrates and commercially available reagents, this reaction affords a synthetically valuable scope that is complimentary to existing methods catalyzed by chiral metal complexes.