N-Iminopyridinium Compounds in Giese Reaction: Photoinduced Homolytic N–N and C–C Bond Cleavage for Cyanoalkyl Radical Generation

We present an innovative photoinduced cyanoalkyl radical addition methodology using N-iminopyridinium reagents derived from cyclic ketones. Mechanistic investigations reveal the association of the excited Hantzsch ester and iminopyridinium with pyridyl radical generation. The ensuing cascade involving homolytic N–N bond and C–C bond cleavage of the pyridyl radical ultimately leads to the formation of cyanoalkyl radical species, leading to diverse Giese-type products. The method showcases versatility and synthetic utility in late-stage functionalization.