Significant Self-Acceleration Effects of Nitrile Additives in the Rhodium-Catalyzed Conversion of Aldoximes to Amides: A New Mechanistic Aspect

Abstract

It was found that the catalytic activity of rhodium complexes was highly sensitive to the type of N-heterocyclic carbene (NHC) ligands in the conversion of aldoximes to amides. Among those species examined, the (cyclooctadiene)rhodium chloride-carbene complex Rh(cod)(IMes)Cl exhibited the highest reactivity when it was employed in combination with a Bronsted acid, thus allowing mild reaction conditions. A significant rate acceleration effect resulting from the addition of nitrite additives was also observed. With the new protocol, the substrate scope of aldoximes has been widely expanded to include sterically congested and electronically varied derivatives. On the basis of detailed mechanistic studies, it is proposed that the reaction proceeds mainly via intramolecular electrophilic addition of aldoxime to rhodium-bound nitrile, which is different from the generally postulated two-step route: dehydration of aldoxime to nitrite followed by hydration of the latter intermediate.