Electrochemical Nonacidic N‐Nitrosation/N‐Nitration of Secondary Amines through a Biradical Coupling Reaction

Abstract An acid‐free N‐nitrosation/nitration of the N−H bonds in secondary amines with Fe(NO 3 ) 3 ⋅ 9H 2 O as the nitroso/nitro source through an electrocatalyzed radical coupling reaction was developed. Cyclic aliphatic amines and N‐heteroaromatic compounds were N‐nitrosated and N‐nitrated, respectively, under mild conditions. Control and competition experiments, as well as kinetic studies, demonstrate that N‐nitrosation and N‐nitration involve two different radical reaction pathways involving N + and N . radicals. Moreover, the electrocatalysis method enables the preferential activation of the N−H bond over the electrode and thus provides high selectivity for specific N atoms. Finally, this strategy exhibits a broad scope and provides a green and straightforward approach to generate useful N ‐nitroso/nitro compounds in good yields. magnified image