Photocatalytic C–H Amination of Aromatics Overcoming Redox Potential Limitations

We report the photocatalytic C–H amination of aromatics overcoming redox potential limitations. Radical cations of aromatic compounds are generated photocatalytically using Ru(phen)3(PF6)2, which has a reduction potential at a high oxidation state (Ered(RuIII/RuII) = +1.37 V vs SCE) lower than the oxidation potentials of aromatic substrates (Eox = +1.65 to +2.27 V vs SCE). The radical cations are trapped with pyridine to give N-arylpyridinium ions, which were converted to aromatic amines.