An Atomically Dispersed Photocatalyst for Undirected <i>para</i> ‐Selective C─H Bond Functionalizations
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.
Article Details
Authors (17)
Suman Pradhan
Department of Chemistry University of Bayreuth Bayreuth Germany
Jun Hu
Peng Ren
Yuman Qin
Department of Chemistry University of Bayreuth Bayreuth Germany
Noopur Jain
EMAT and NANOlab Center of Excellence Department of Physics University of Antwerp Antwerp 2020 Belgium
Susanna Monti
CNR-ICCOM, Institute of Chemistry of Organometallic Compounds
Giovanni Barcaro
CNR-IPCF, Institute of Chemical and Physical Processes
Aleksander Jaworski
Department of Chemistry
Xingchao Dai
Leibniz-Institut für Katalyse, Albert-Einstein-Str. 29A, Rostock 18059, Germany
Jabor Rabeah
Magnetic Resonance and X-ray Methods
Joaquin Silvestre‐Albero
Departamento de Química Inorgánica Instituto Universitario de Materiales Universidad de Alicante Alicante E‐03080 Spain
Veronica Celorrio
Diamond Light Source Ltd., Harwell Science & Innovation Campus, Didcot OX11 0DE, U.K.
Anna Rokicińska
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland
Piotr Kuśtrowski
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland
Sandra Van Aert
EMAT and NANOlab Center of Excellence Department of Physics University of Antwerp Antwerp 2020 Belgium
Sara Bals
Electron Microscopy for Materials Research and NanoLight Center of Excellence, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium
Shoubhik Das
Department of Chemistry, University of Bayreuth, Universitätsstraße 30, 95447 Bayreuth, Germany