title: Synthesis of asymmetric peroxides: transition metal (Cu, Fe, Mn, Co) catalyzed peroxidation of beta-dicarbonyl compounds with tert-butyl hydroperoxide.
abstract: The transition metal (Cu, Fe, Mn, Co) catalyzed peroxidation of beta-dicarbonyl compounds at the alpha 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%).
authors.affiliation: N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation. terentev@ioc.ac.ru
authors.forename: Alexander O
authors.initials: AO
authors.lastname: Terent'ev
authors.forename: Dmitry A
authors.initials: DA
authors.lastname: Borisov
authors.forename: Ivan A
authors.initials: IA
authors.lastname: Yaremenko
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Chernyshev
authors.forename: Gennady I
authors.initials: GI
authors.lastname: Nikishin
mesh_terms: D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry*; D020122:tert-Butylhydroperoxide / Q000737:chemistry*
chemical_list: D007659:Ketones; D010545:Peroxides; D028561:Transition Elements; D020122:tert-Butylhydroperoxide