Visible-Light-Induced Photoredox Catalysis of Dye-Sensitized Titanium Dioxide: Selective Aerobic Oxidation of Organic Sulfides

TiO2 photoredox catalysis has recently attracted much interest for use in performing challenging organic transformations under mild reaction conditions. However, the reaction scheme is hampered by the fact that TiO2 can only be excited by UV light of wavelengths shorter than 385nm. One promising strategy to overcome this issue is to anchor an organic, preferably metal-free dye onto the surface of TiO2. Importantly, we observed that the introduction of a catalytic amount of the redox mediator TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl] ensured the stability of the anchored dye, alizarin redS, thereby resulting in the selective oxidation of organic sulfides with O-2. This result affirms the essential role of the redox mediator in enabling the organic transformations by visible-light photoredox catalysis.