Photoredox-Catalyzed Cross-Coupling of In Situ Generated Quinoxalinones with Indoles for the Synthesis of Tertiary Alcohols

A visible light-driven photoredox-catalyzed direct C(sp²)-H functionalization of N-H free indoles with quinoxalinones generated in situ from 2,2-dihydroxy-1<i>H</i>-indene-1,3(2<i>H</i>)-dione and phenylene-1,2-diamines has been reported with the aid of Na₂-Eosin Y as the photocatalyst and the Hünig base as the sacrificial electron and proton donor. The reaction provides easy access to a variety of quaternary-centered C-3 selective indole-substituted tertiary alcohols in good yields. Mechanistic studies demonstrated the realization of photoredox-catalyzed in situ quinoxalinone formation and their proton-coupled single electron reduction to the corresponding ketyl radicals followed by cross-coupling with indoles. The potential applications of the synthesized tertiary alcohols in photoacid-catalyzed carbon-carbon and carbon-sulfur bond-forming reactions feature the key findings of the present work.