An Atomically Dispersed Photocatalyst for Undirected para‐Selective C–H bond Functionalizations

Titelangaben

Pradhan, Suman ; Hu, Jun ; Ren, Peng ; Qin, Yuman ; Jain, Noopur ; Monti, Susanna ; Barcaro, Giovanni ; Jaworski, Aleksander ; Dai, Xingchao ; Rabeah, Jabor ; Silvestre-Albero, Joaquin ; Celorrio, Veronica ; Rokicińska, Anna ; Kuśtrowski, Piotr ; Van Aert, Sandra ; Bals, Sara ; Das, Shoubhik:
An Atomically Dispersed Photocatalyst for Undirected para‐Selective C–H bond Functionalizations.
In: Angewandte Chemie International Edition. Bd. 64 (2025) Heft 33 . - e202508512.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.202508512

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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 meta-directing aromatics (-NO2, -CF3, -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.