Advances in C−N Bond Formation via <i>N</i>‐Centered Radicals from <i>N</i>‐Aminopyridinium Reagents

Abstract Nitrogen‐centered radicals (NCRs) have gained significant attention due to their high reactivity, which facilitates many useful and challenging transformations, particularly in the formation of C−N bonds. In this regard, N ‐aminopridinium reagents are easily accessible substrates that readily generate N ‐centered radicals, which can be trapped by arenes, olefins, alkynes and even alkanes under visible light irradiation. In recent years, amination strategies involving N ‐aminopyridinium salts have grown remarkably and attracted considerable interest within the synthetic community. This review comprehensively includes all the significant advances in C−N bond construction via N ‐centered radicals derived from N ‐aminopyridinium substrates.