An Atomically Dispersed Photocatalyst for Undirected <i>para</i> ‐Selective C─H Bond Functionalizations
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.
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
- Published
- 2025-06-11
- DOI
- https://doi.org/10.1002/ange.202508512
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00