A Mild, Catalytic, and Highly Selective Method for the Oxidation of α,β-Enones to 1,4-Enediones

2003-02-21T00:00:00Z (GMT) by Jin-Quan Yu E. J. Corey
A new and simple method is described for the one-step oxidation of α,β-enones to 1,4-enediones in good yields (generally 80−90%) using <i>t</i>-butylhydroperoxide as stoichiometric oxidant and 20% Pd(OH)<sub>2</sub> on carbon (5 mol %) as catalyst in CH<sub>2</sub>Cl<sub>2</sub> solution. The same reagents have been used to convert ethylene ketals of α,β-enones to the corresponding monoethylene ketals of 1,4-enediones. Seven representative examples are presented in Table . All of the available evidence on these oxidations points to a radical-chain mechanism initiated by the <i>tert</i>-butylperoxy radical (see Scheme ). γ-<i>tert</i>-Butylperoxy ethers are formed as major products in the oxidation of α,β-enones possessing only a single γ-hydrogen.