α,β-Unsaturated oximes underwent electrophilic epoxidation with in-situ-generated dimethyldioxirane to give the corresponding epoxides in good yields. This reaction is an example of "carbonyl umpolung" by transformation of α,β-unsaturated ketones to their oximes. Nucleophilic ring-opening reactions of the epoxides afforded α-substituted products. Shi asymmetric epoxidation of the oximes proceeded with moderate enantioselectivity.
Keywords: Shi asymmetric epoxidation; dimethyldioxirane; epoxidation; umpolung; α,β-unsaturated oxime.