Photoinduced Decarboxylative Radical Coupling Reaction of Multiply Oxygenated Structures by Catalysis of Pt-Doped TiO2

• Published in: Journal of organic chemistry 2022-01, Vol.87 (1), p.730-736
• Main Authors: Kuwana, Daiki, Komori, Yuma, Nagatomo, Masanori, Inoue, Masayuki
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.1c02736

A new reaction system was devised for decarboxylative radical coupling reactions by heterogeneous semiconductor photoredox catalysis. When an α-alkoxy carboxylic acid and Pt-doped TiO2 in EtOAc were irradiated with a violet light-emitting diode at room temperature, the photogenerated electron hole of TiO2 oxidatively induced the ejection of CO2 via the formation of a carboxyl radical to produce the corresponding α-alkoxy radical. C­(sp3)–C­(sp3) bond formation between the radicals led to dimers with reductive conversion of protons to H2 by the photogenerated electron. Alternatively, in the presence of an electron-deficient olefin, an intermolecular radical addition reaction occurred, resulting in the formation of a 1,4-adduct via single-electron reduction and subsequent protonation. These operationally simple and mild transformations are amenable to the one-step assembly of densely oxygenated linear and branched carbon chains.