Sustainable Chemistry: A Single-Atom Copper Photocatalyst Opens New Pathways for Selective N-Demethylation
An international research consortium has developed an innovative heterogeneous single-atom copper photocatalyst supported on functionalized graphitic carbon nitride (Cu@f-gC3N4). The study, published in the journal Nature Communications, describes an efficient methodology for the selective N-demethylation of aliphatic and aromatic tertiary amines. Operating under exceptionally mild conditions with visible-light irradiation, the system utilizes molecular oxygen as the terminal oxidant. This technology provides a clean alternative to classical protocols and homogeneous photoredox systems, eliminating reliance on expensive noble-metal catalysts and toxic sacrificial additives.
The photocatalyst demonstrated high operational robustness, enabling the reaction to be performed on a 10 mmol scale while maintaining excellent structural stability, thereby allowing catalyst recovery and reuse over more than 10 consecutive cycles without significant loss of activity. The contributions of CNR researchers Susanna Monti (CNR-ICCOM) and Giovanni Barcaro (CNR-IPCF) provided important support for validating the experimental models and describing the molecular mechanism of the reaction. Through molecular dynamics simulations and quantum-chemical calculations, the CNR team validated the experimental models and elucidated the atomistic reaction pathway, demonstrating how the isolated copper sites and the 2D matrix of the functionalized Cu@f-gC3N4 work cooperatively to facilitate photoinduced charge separation, oxygen activation, and final substrate hydrolysis.
Su, Wenhao; Pradhan, Suman; Hu, Jun; Ren, Peng; Rockstroh, Nils; Skorynina, Alina; Kuśtrowski, Piotr; Monti, Susanna; Barcaro, Giovanni; Zeng, Chaoqin; Rabeah, Jabor; Jaworski, Aleksander; Simonelli, Laura; Slabon, Adam; Das, Shoubhik. An Atomically Dispersed Copper-Catalyst Lights the Way to Selective N-Demethylations. Nature Communications 2026, 17, 8489.
More information at: https://www.cnr.it/it/news/14574