Selective Phenol Hydrogenation to Cyclohexanone Over a Dual Supported Pd–Lewis Acid Catalyst

Abstract

Cooperative Reduction Selective redox transformation remains a general challenge in chemical synthesis. All too often, the most readily available precursor to a compound must be over-reduced (or over-oxidized) and then carefully coaxed back to a desired intermediate state. Such is the case with the synthesis of cyclohexanone, which is mass-produced for use in the preparation of nylon: Access by direct reduction of phenol is plagued by the rapid addition of too many hydrogen atoms to the substrate, producing an alcohol (cyclohexanol) in place of the ketone. Liu et al. (p. 1250 ) have discovered that the unexpected cooperation of supported palladium and a Lewis acid such as aluminum trichloride—two catalysts widely used alone but rarely in concert—facilitates highly selective conversion of phenol to cyclohexanone near room temperature. The key appears to be inhibition of the undesired ketone-to-alcohol reduction step by the Lewis acid.