Copper-Catalyzed Oxidative Esterification and Amidation of Benzylic Hydrocarbons

A new and efficient methodology has been developed using a Copper-DMAP complex to perform C-O and C-N bond-forming cross-coupling reactions. The catalyst enables atom-economic esterification, amidation, and sulfamidation of benzylic C-H bonds using benzoic acids, benzamides, and sulfonamides employing di-tert-butyl peroxide (DTBP) as the oxidant. The air-stable and easy-to-prepare complex with low catalyst loading enables the base- and ligand-free synthesis of a variety of benzyl esters, N-benzyl benzamides, and N-benzyl aryl sulfonamides in open-air conditions with good to excellent yields within a short reaction time.