Stereoretentive Decarboxylative Amidation of α,β-Unsaturated Carboxylic Acids to Access Enamides

Abstract

Enamides have emerged as robust alternatives for enamines, exhibiting versatile reactivity for further synthetic modifications, including nucleophilic addition, cycloaddition, and asymmetric hydrogenation. While transition-metal-catalyzed cross-coupling of alkenyl (pseudo)halides with amides has been widely employed to construct this valuable scaffold, it suffers from some limitations, such as the need for transition-metal catalysts and the preparative synthesis of alkenyl (pseudo)halides. In this study, we report a mild and convenient stereoretentive decarboxylative amidation of alpha,beta-unsaturated carboxylic acids with easily procurable 1,4,2-dioxazol-5-ones, providing a practical synthetic route to enamides. Density functional theory (DFT) calculations revealed a plausible reaction mechanism, which involves the nucleophilic addition of a carboxylate onto dioxazolone, followed by sequential concerted rearrangements.