Selective photocatalytic reactions with organic photocatalysts

Abstract

Selective photocatalytic oxygenation of various substrates has been achieved using organic photocatalysts via photoinduced electron-transfer reactions of photocatalysts with substrates and dioxygen under visible light irradiation. Photoinduced electron transfer from benzene to the singlet-excited state of the 3-cyano-1-methylquinolinium ion has enabled the oxidation of benzene by dioxygen with water to yield phenol selectively. Alkoxybenzenes were obtained when water was replaced by alcohols under otherwise the same experimental conditions. Photocatalytic selective oxygenation reactions of aromatic compounds have also been achieved using an electron donor–acceptor linked dyad, 9-mesityl-10-methylacridinium ion (Acr⁺–Mes) acting as a photocatalyst and dioxygen as an oxidant under visible light irradiation. The oxygenation reaction is initiated by intramolecular photoinduced electron transfer from the mesitylene moiety to the singlet-excited state of the acridinium moiety of Acr⁺–Mes to afford an extremely long-lived electron-transfer state. The electron-transfer state can oxidize and reduce substrates and dioxygen, respectively, leading to selective oxygenation and halogenation of substrates. C–C bond formation of substrates has also been made possible by using Acr⁺–Mes as a photocatalyst.