An Atomically Dispersed Photocatalyst for Undirected <i>para</i> ‐Selective C─H Bond Functionalizations
Suman Pradhan, Jun Hu, Peng Ren, Yuman Qin, Noopur Jain, Susanna Monti, Giovanni Barcaro, Aleksander Jaworski, Xingchao Dai, Jabor Rabeah, Joaquín Silvestre‐Albero, Verónica Celorrio, Anna Rokicińska, Piotr Kuśtrowski, Sandra Van Aert, Sara Bals, Shoubhik Das
Abstract
Abstract Regioselective C─H bond functionalization is pivotal in modern scientific exploration, offering solutions for achieving novel synthetic methodologies and pharmaceutical development. In this aspect, achieving exceptional regioselective functionalization, like para ‐selective products in electron‐poor aromatics, diverges from traditional methods. Leveraging the advantages of atomically dispersed photocatalysts, we designed a robust photocatalyst for an unconventional regioselective aromatic C─H bond functionalization. This innovation enabled para ‐selective trifluoromethylations of electron‐deficient metadirecting aromatics (─NO 2 , ─CF 3 , ─CN, etc.), which is entirely orthogonal to the traditional approaches. Mechanistic experiments and DFT analysis confirmed the interaction between Cu‐atom and the aromatic substrate, alongside the photocatalyst's molecular arrangement, driving selective exposure of the para ‐selective functionalization. This strategic approach elucidated pathways for precise molecular transformations, advancing the frontier of regioselective C─H bond functionalization by using atomically dispersed photocatalysts in organic synthesis.