Iridium-catalyzed reductive nucleophilic addition to tertiary amides

Abstract

This article describes the development of an iridium-catalyzed reductive nucleophilic addition to tertiary amides. A conspicuous feature of this reaction is its high amide-selectivity via two processes: i) chemoselective hydrosilylation of amide carbonyls with Vaska’s complex [IrCl(CO)(PPh3)2] and (Me2HSi)2O, and ii) subsequent addition of a variety of mild nucleophiles to the resulting electrophilic iminium ions by the assistance of an acid. The reaction takes place in the presence of a variety of functional groups such as ester and nitro groups.