Visible-Light-Induced Cascade Difunctionalization of Indoles Enabled by the Synergy of Photoredox and Photoexcited Ketones: Direct Access to Alkylated Pyrrolophenanthridones

Herein, we describe a methodology to construct polycyclic pyrrolophenanthridones with an (amino)alkyl side chain that involves visible-light-induced decarboxylative radical addition for the intermolecular dearomatization of indoles and subsequent photoinduced C(sp2)-X bond activation via photoexcited ketones for an intramolecular cyclization cascade. Carboxylic acids serve both as a radical source toward indole dearomatization and as reductants to initiate an electron transfer with photoexcited N-acylindole derivatives in the reaction toward pyrrolophenantridone skeletons, which occurs under mild reaction conditions with good functional group tolerance. © 2022 American Chemical Society.