Radical Cation Diels-Alder Reactions by TiO Photocatalysis

Radical cation Diels-Alder reactions by titanium dioxide (TiO) photocatalysis in lithium perchlorate/nitromethane solution are described. TiO photocatalysis promotes reactions between electron-rich dienes and dienophiles, which would otherwise be difficult to accomplish due to electronic mismatching. The reactions are triggered by hole oxidation of the dienophile and are completed by the excited electron reduction of the radical cation intermediate at the dispersed surface in the absence of any sacrificial substrate.