We describe here an oxidant-free strategy to synthesize indoles, i.e., under visible-light irradiation (λ = 450 nm), catalytic amounts of an iridium(III) photosensitizer and cobaloxime catalyst transform various N-aryl enamines exclusively into indoles. Our methodology affords indoles in good to excellent yields under mild reaction conditions and produces H2 as the only byproduct. Spectroscopic and electrochemical studies verify that the designed system proceeds via visible-light-catalyzed oxidation of N-aryl enamines, followed by intramolecular radical addition to yield the indoles smoothly under ambient conditions. ACS Catal., 2016, 6, pp 4635–4639 |