Hydrogen Bond-Mediated Transition Metal-Free Alcoholysis of Primary Amides to Access Esters

An efficient hydrogen bond-mediated alcoholysis of primary amides was disclosed using diethyl phosphonate (DEP) as a catalyst. In this process, a wide range of primary amides and alcohols were tested and smoothly transformed to corresponding esters in moderate to good yields. This novel strategy features transition metal-free, broad substrate scope and a hydrogen bond-mediated one-pot pathway. In addition, the reaction showed a highly chemoselective o/alcoholic o-acylation of mercapto/phenolic alcohols.