Synthesis of Asymmetric Peroxides: Transition Metal (Cu, Fe, Mn, Co) Catalyzed Peroxidation of β-Dicarbonyl Compounds with tert-Butyl Hydroperoxide

The transition metal (Cu, Fe, Mn, Co) catalyzed peroxidation of beta-dicarbonyl compounds at the a. position by tert-butyl hydroperoxide was discovered. A selective, experimentally convenient, and gram-scale method was developed for the synthesis of alpha-peroxidated derivatives of beta-diketones, beta-keto esters, and diethyl malonate. Virtually stoichiometric (2-3/1) molar ratios of tert-butyl hydroperoxide and a dicarbonyl compound were used in the reactions with beta-diketones and beta-keto esters. The target compounds were synthesized in the highest yields from beta-keto esters (45-90%) and in somewhat lower yields from beta-diketones (46-75%) and malonates (37-67%).