Tunable Pd/C-catalyzed oxidative alkoxycarbonylation/aminocarbonylation of aryl hydrazines with alcohols/inert tertiary amines through C–N bond activation

Abstract

We report Pd/C-catalyzed oxidative aminocarbonylation and alkoxycarbonylation of unactivated aryl hydrazines. This protocol employs inert tertiary amines as an aminal source and arylhydrazines via oxidative sp³ and sp² C–N bond activation using molecular oxygen as an oxidant. The tertiary amine acts as both a nucleophile and a base. Advantageously, this process involves Pd/C as a heterogeneous and recyclable catalyst, and propylene carbonate as an environmentally benign solvent. This established protocol provides a promising, simple, and effective approach for preparing esters and tertiary amides under co-catalyst-free and moisture sensitive ligand-free conditions. This catalytic process features sustainable and resourceful, recyclable, and valuable products.