title: A mild, catalytic, and highly selective method for the oxidation of alpha,beta-enones to 1,4-enediones.
abstract: A new and simple method is described for the one-step oxidation of alpha,beta-enones to 1,4-enediones in good yields (generally 80-90%) using t-butylhydroperoxide as stoichiometric oxidant and 20% Pd(OH)2 on carbon (5 mol %) as catalyst in CH2Cl2 solution. The same reagents have been used to convert ethylene ketals of alpha,beta-enones to the corresponding monoethylene ketals of 1,4-enediones. Seven representative examples are presented in Table 1. All of the available evidence on these oxidations points to a radical-chain mechanism initiated by the tert-butylperoxy radical (see Scheme 1). gamma-tert-Butylperoxy ethers are formed as major products in the oxidation of alpha,beta-enones possessing only a single gamma-hydrogen.
authors.affiliation: Department of Chemistry, Cambridge University, Cambridge CB2 1EW, United Kingdom.
authors.forename: Jin-Quan
authors.initials: JQ
authors.lastname: Yu
authors.forename: E J
authors.initials: EJ
authors.lastname: Corey
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D006878:Hydroxides / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D020122:tert-Butylhydroperoxide / Q000737:chemistry
chemical_list: D000475:Alkenes; D006878:Hydroxides; D007659:Ketones; D010165:Palladium; D020122:tert-Butylhydroperoxide