title: Visible light-mediated atom transfer radical addition via oxidative and reductive quenching of photocatalysts.
abstract: Herein, the development of visible light-mediated atom transfer radical addition (ATRA) of haloalkanes onto alkenes and alkynes using the reductive and oxidative quenching of [Ir{dF(CF(3))ppy}(2)(dtbbpy)]PF(6) and [Ru(bpy)(3)]Cl(2) is presented. Initial investigations indicated that the oxidative quenching of photocatalysts could effectively be utilized for ATRA, and since that report, the protocol has been expanded by broadening the scope of the reaction in terms of the photocatalysts, substrates, and solvents. In addition, further modifications of the reaction conditions allowed for the efficient ATRA of perfluoroalkyl iodides onto alkenes and alkynes utilizing the reductive quenching cycle of [Ru(bpy)(3)]Cl(2) with sodium ascorbate as the sacrificial electron donor. These results signify the complementary nature of the oxidative and reductive quenching pathways of photocatalysts and the ability to predictably direct reaction outcome through modification of the reaction conditions.
authors.affiliation: Department of Chemistry, Boston University, Boston, Massachusetts 02215, USA.
authors.forename: Carl-Johan
authors.initials: CJ
authors.lastname: Wallentin
authors.forename: John D
authors.initials: JD
authors.lastname: Nguyen
authors.forename: Peter
authors.initials: P
authors.lastname: Finkbeiner
authors.forename: Corey R J
authors.initials: CR
authors.lastname: Stephenson
mesh_terms: D000475:Alkenes / Q000737:chemistry; D000478:Alkylation; D000480:Alkynes / Q000737:chemistry; D002384:Catalysis; D005609:Free Radicals / Q000737:chemistry; D054879:Halogenation; D008027:Light; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D012997:Solvents / Q000737:chemistry
chemical_list: D000475:Alkenes; D000480:Alkynes; D005609:Free Radicals; D012997:Solvents