Copper‐Catalyzed Oxidative Esterification and Amidation of Benzylic Hydrocarbons

Abstract 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.