Mn-Catalyzed Aerobic Oxidative α-Cyanation of Tertiary Amines Using Azo/Hydrazide Redox.

Azo compounds such as diethyl azodicarboxylate have been used in oxidative coupling reactions to generate iminium ions from tertiary amines. However, the requirement of stoichiometric amounts of azo compounds limits their large-scale applications. Herein, we present an aerobic oxidative α-cyanation of tertiary amines using catalytic amounts of an azo compound or hydrazine. The developed protocol provides a practical and ecofriendly route for α-cyanated tertiary amines, using molecular oxygen as the terminal oxidant.