An Atomically Dispersed Photocatalyst for Undirected <i>para</i> ‐Selective C─H Bond Functionalizations
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<sub>2</sub>, ─CF<sub>3</sub>, ─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.
Authors
- Sara Bals (ORCID: https://orcid.org/0000-0002-4249-8017)
- Peng Ren (ORCID: https://orcid.org/0000-0002-5767-2938)
- Verónica Celorrio (ORCID: https://orcid.org/0000-0002-2818-3844)
- Xingchao Dai (ORCID: https://orcid.org/0000-0002-9623-3743)
- Piotr Kuśtrowski (ORCID: https://orcid.org/0000-0001-8496-0559)
- Jabor Rabeah (ORCID: https://orcid.org/0000-0003-2162-0981)
- Shoubhik Das (ORCID: https://orcid.org/0000-0002-4577-438X)
- Noopur Jain (ORCID: https://orcid.org/0000-0003-4934-9070)
- Suman Pradhan (ORCID: https://orcid.org/0000-0002-5942-3206)
- Giovanni Barcaro (ORCID: https://orcid.org/0000-0002-5520-5914)
- Yuman Qin (ORCID: https://orcid.org/0009-0006-0050-5043)
- Susanna Monti (ORCID: https://orcid.org/0000-0002-3419-7118)
- Joaquín Silvestre‐Albero (ORCID: https://orcid.org/0000-0002-0303-0817)
- Aleksander Jaworski (ORCID: https://orcid.org/0000-0002-7156-559X)
- Anna Rokicińska (ORCID: https://orcid.org/0000-0001-8397-4422)
- Sandra Van Aert (ORCID: https://orcid.org/0000-0001-9603-8764)
- Jun Hu (ORCID: https://orcid.org/0009-0007-5212-0839)
Institutions
- Jagiellonian University (PL)
- University of Alicante (ES)
- University of Antwerp (BE)
- Stockholm University (SE)
- Diamond Light Source (GB)
- Lanzhou Institute of Chemical Physics (CN)
- Leibniz Institute for Catalysis (DE)
- Institute for the Chemistry of OrganoMetallic Compounds (IT)
- Institute for Chemical and Physical Processes (IT)
- University of Bayreuth (DE)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-06-11
- DOI
- https://doi.org/10.1002/anie.202508512
- Citations
- 5
- Primary Topic
- Catalytic C–H Functionalization Methods
- Type
- article
- Field-Weighted Citation Impact
- 4.68
Funders
- Generalitat Valenciana
- China Scholarship Council