The reaction mechanism of palladium-catalyzed visible light-driven carboxylation of aryl halides and triflates with a photoredox catalyst was examined in detail. Experimental and theoretical studies indicated that the active species for photoredox-catalyzed reduction was cationic ArPd(II)+ species to generate nucleophilic ArPd(I) or its further reduced ArPd(0)− species, which reacted with CO2 to give carboxylic acids. Hydrodehalogenated compounds, main byproducts in this carboxylation, were thought to be generated by protonation of these reduced species.
Mechanistic Studies into Visible Light-Driven Carboxylation of Aryl Halides/Triflates by the Combined Use of Palladium and Photoredox Catalysts
Bull. Chem. Soc. Jpn. 2021, 94 (7), 1846-1853, DOI: 10.1246/bcsj.20210151.