Synthetic Approaches for C-N Bonds by TiO₂ Photocatalysis

Nitrogen-containing organic compounds possess the most important status in drug molecules and agricultural chemicals. More than 80% currently used drugs have at least a C-N bond. The green and mild methodology to prepare diverse C-N bonds to replace traditional harsh preparation protocols is always a hotspot in modern synthetic chemistry. TiO₂-based nanomaterials, considered as environmentally benign, stable, and powerful photocatalysts, have recently been applied in some certain challenging organic synthesis including construction of useful C-N compounds under mild conditions that are impossible to complete by conventional catalysis. This mini review would present state-of-the-art paragon examples of TiO₂ photocatalyzed C-N bond formations. The discussion would be divided into two main sections: (1) N-alkylation of amines and (2) C-N formation in heterocycle synthesis. Especially, the mechanism of TiO₂ photocatalytic C-N bond formation through activating alcohol into C=O by photo-induced hole followed by C=NH-R formation and finally hydrogenating C=NH-R into C-N bonds by combination of photo-induced electron/H⁺ assisted with loaded-Pt would be covered in detail. We believe that the mini-review will bring new insights into TiO₂ photocatalysis applied to construct challenging organic compounds through enabling photo-induced hole and electron in a concerted way on coupling two substrate molecules together with respect to their conventionally independent catalysis behavior.