title: Photocatalytic fluoroalkylation reactions of organic compounds.
abstract: Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, laboratory-available and inexpensive photoorgano catalysts (POC), in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critical account of transition metal and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.
authors.affiliation: Departamento de Química Orgánica, Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 954 CP 1113, Buenos Aires, Argentina. apostigo@ffyb.uba.ar.
authors.forename: Sebastián
authors.initials: S
authors.lastname: Barata-Vallejo
authors.affiliation: Departamento de Química Orgánica, CIHIDECAR-CONICET, Pabellón II, 3er piso, Ciudad Universitaria, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428, Buenos Aires, Argentina.
authors.forename: Sergio M
authors.initials: SM
authors.lastname: Bonesi
authors.affiliation: Departamento de Química Orgánica, Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 954 CP 1113, Buenos Aires, Argentina. apostigo@ffyb.uba.ar.
authors.forename: Al
authors.initials: A
authors.lastname: Postigo
mesh_terms: D000477:Alkylating Agents / Q000737:chemistry; D000478:Alkylation; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D054879:Halogenation; D007495:Iridium / Q000737:chemistry*; D008027:Light; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D012428:Ruthenium / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D000477:Alkylating Agents; D056831:Coordination Complexes; D005609:Free Radicals; D028561:Transition Elements; D007495:Iridium; D012428:Ruthenium