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Ligand‐Enabled Photoinduced Ruthenium Catalysis for Ortho ‐C─O Bond Formation at Room Temperature
Author(s) -
Sivaraj Chandrasekaran,
Udayan Ajay Thonipalliyalil,
Muthuvel Karthick,
Gandhi Thirumanavelan
Publication year - 2025
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202500711
Abstract Photoinduced ruthenium‐catalyzed ortho ‐benzoxylation through organophosphine ligand is unveiled. The in situ generation of the organophosphine‐ruthenium complex facilitates ligand‐to‐metal charge transfer (LMCT) under visible light, promoting the site‐selective ortho ‐benzoxylation at room temperature. The broad scope of aryl, aliphatic, and heterocyclic carboxylic acids are key attractions of this methodology. EPR and UV‐Vis analysis support a LMCT process between a photoexcited organophosphine and Ru‐complex under blue‐light irradiation. Comprehensive mechanistic investigation highlights the role of light, ligands, oxidants, the LMCT process, and the unique reactivity of the directing group.