Late-stage electron-catalyzed perfluoroalkylation of coumarin derivatives—Thermal fluoroalkyl radical production from sodium perfluoroalkyl sulfinate salts

• Published in: Journal of fluorine chemistry Vol. 197; pp. 42 - 48
• Main Authors: Torviso, M. Rosario, Mansilla, Daniela, Garcia, Selva, Lantaño, Beatriz, Barata-Vallejo, Sebastian, Postigo, Al
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.05.2017; Elsevier; Elsevier BV
• Subjects: 3-perfluoroalkylated coumarin; Anthraquinone; Chemical synthesis; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Coumarin; Derivatives; Electron-catalyzed; Electrons; Iodides; Perfluoroalkylation; Photocatalysis; Physical Sciences; Potassium oxalate; Salt; Salts; Science & Technology; Sodium; Solvents; Studies; Sulfonic acid; Perfluoroalkylation; 3-perfluoroalkylated coumarin; Coumarin; Electron-catalyzed; Photocatalysis; Potassium oxalate; REAGENTS; FLUORESCENT DYES; ORGANIC-COMPOUNDS; GENERATION; TRIFLUOROMETHYLATION
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2017.03.005

[Display omitted] •Electron-catalyzed process for the radical perfluoroalkylation of coumarin derivatives where a radical anion intermediate is proposed.•Photocatalyzed perfluoroalkylation of coumarin derivatives.•Sodium perfluoroalkylsulfinate salts. Novel and high-yielding protocols for the late-stage synthesis of 3-perfluoroalkyl-substituted coumarin derivatives employing either perfluoroalkyl iodides RFI or sodium perfluoroalkylsulfinate salts NaSO2RF as perfluoroalkyl RF radical precursors is presented. The electron-catalyzed methodologies make use of two comparative and parallel protocols as an entry to the production of RF radicals: (i) from NaSO2Rf sources and the thermal tert-butylhydroperoxide (TBHP) radical initiation in MeCN: CH2Cl2 as organic solvent mixture, and (ii) from commercial RFI and the photoorganocatalyst anthraquinone-2-sulfonic acid as the room-light initiation process in DMF: CH2Cl2 as mixture of solvents.