The Rose Bengal-photocatalyzed perfluorohexylation of olefins, alkynes, and electron-rich aromatic compounds in water was achieved employing perfluorohexyl iodide as fluoroalkyl source and TMEDA as sacrificial donor under green LED irradiation. Alkenes and alkynes rendered products derived from the atom transfer radical addition (ATRA) pathway, and in the case of alkynes, exclusively as E-stereoisomers. These are the first examples of photocatalyzed ATRA reactions carried out excursively in water alone. The reactions of aromatic compounds under the current protocol in water present the advantage of employing a perfluoroalkyl iodide (C6F13-I) as source of perfluorohexyl radicals. Examples of photocatalytic late-stage incorporations of fluoroalkyl moieties into two commercial drugs of widespread use are reported.
Keywords: Late-stage perfluoroalkylation; Perfluoroalkylation of alkynes; Perfluoroalkylation of arenes; Perfluoroalkylation of olefins; Photocatalysis in water; Photocatalytic perfluoroalkylation; Photocatalyzed ATRA reactions.
© 2021. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.