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Communication

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

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Jin-Quan Yu^† and E. J. Corey*^‡

Department of Chemistry, Cambridge University, Cambridge CB2 1EW, United Kingdom, and Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138

J. Am. Chem. Soc., 2003, 125 (11), pp 3232–3233

DOI: 10.1021/ja0340735

Publication Date (Web): February 21, 2003

†

Cambridge University.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

‡

Harvard University.

, corey@chemistry.harvard.edu

Abstract

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 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 α,β-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). γ-tert-Butylperoxy ethers are formed as major products in the oxidation of α,β-enones possessing only a single γ-hydrogen.

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History

Published In Issue March 19, 2003
Received January 8, 2003

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Communication

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