Visible-Light-Induced Nitrogen-Atom Deletion of Unactivated Secondary Amines

Single-atom deletion has emerged as a powerful strategy for C-C bond formation, but existing methods are largely restricted to benzylic substrates, limiting their broader synthetic utility. Here, we report a visible-light-induced nitrogen-atom deletion of unactivated secondary amines. This transformation enables the efficient construction of general C(sp³)-C(sp³) linkages directly from readily available C-N bonds, introducing atom deletion as a practical disconnection strategy in retrosynthetic design. The protocol applies to a wide range of N-heterocycles, converting them into the corresponding N-deleted carbocycles and heterocycles, and thereby streamlining access to pharmaceutically relevant yet previously inaccessible molecular scaffolds. Mechanistic studies reveal that visible light directly excites isodiazenes, redirecting their reactivity from N atom insertion toward N atom deletion. This discovery provides unprecedented control over isodiazene chemistry and unlocks opportunities for divergent skeletal editing. Overall, this work introduces a general platform for nonbenzylic C-C bond formation and a versatile approach to nitrogen-based skeletal editing, expanding the synthetic toolbox for organic synthesis, medicinal chemistry, and chemical biology.