Nitrogen‐Centered Radical‐Directed C(sp ³ )−H Amination and Aminoalkylation Using (Diarylmethylene)amino Benziodoxolones

Intermolecular C(sp 3 )−H functionalization via nitrogen‐centered radical‐directed 1,5‐hydrogen atom transfer (HAT) is a powerful strategy for rapidly constructing functionalized molecules. Despite the obvious potential, applying this approach to aminofunctionalization remains challenging. Herein, a photochemical method is reported for C(sp 3 )−H aminofunctionalization that is achieved using hypervalent iodine‐based aminating reagents—(diarylmethylene)amino benziodoxolones (DABXs). These reagents act as both single‐electron oxidants and sources of nitrogen‐based SOMOphiles (iminyl radicals), which enables the site‐selective amination and aminoalkylation of α ‐aminoxy acid derivatives via 1,5‐HAT. Notably, this reaction proceeds efficiently under mild reaction conditions without external photosensitizers to offer a practical and versatile method for the syntheses of readily modifiable diamines and aminoamides.