Catalytic Ester−Amide Exchange Using Group (IV) Metal Alkoxide−Activator Complexes

Abstract
A process for preparation of amides from unactivated esters and amines has been developed using a catalytic system comprised of group (IV) metal alkoxides in conjunction with additives including 1-hydroxy-7-azabenzotriazole (HOAt). In general, ester−amide exchange proceeds using a variety of structurally diverse esters and amines without azeotropic reflux to remove the alcohol byproduct. Initial mechanistic studies on the Zr(Ot-Bu)4−HOAt system revealed that the active catalyst is a novel, dimeric zirconium complex as determined by X-ray crystallography.

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