An unprecedented visible-light photoredox-catalyzed iminyl radical formation by N-H cleavage with H release has been developed. Its application in the synthesis of various isoquinolines and related polyaromatics in high atom economy at ambient temperature by applying a photosensitizer, Acr-Mes ClO, and a new cobalt catalyst, Co(dmgH)(4-CONMePy)Cl is reported. Mechanistic investigations indicated that the generated iminyl radical initiates the cascade C-N/C-C bonds formation and the catalytic cycle occurs by a simultaneous oxidative as well as reductive quenching pathway.
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