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 der Verlagsversion: https://doi.org/10.1002/anie.202508512

Volltext

	Format: PDF Name: Angew Chem Int Ed - 2025 - Pradhan - An Atomically Dispersed Photocatalyst for Undirected para‐Selective C H Bond.pdf Version: Veröffentlichte Version Verfügbar mit der Lizenz Creative Commons BY 4.0: Namensnennung
	Download (4MB)

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.