Combining Flavin Photocatalysis and Organocatalysis: Metal-Free Aerobic Oxidation of Unactivated Benzylic Substrates

We report a system with ethylene-bridged flavinium salt 2b which catalyzes the aerobic oxidation of toluenes and benzyl alcohols with high oxidation potential (E-ox > +2.5 V vs SCE) to give the corresponding benzoic acids under visible light irradiation. This is caused by the high oxidizing power of excited 2b (E(2b*) = +2.67 V vs SCE) involved in photooxidation and by the accompanying dark organocatalytic oxygenation provided by the in situ formed flavin hydroperoxide 2b-OOH.