Visible-Light Reductive Cyclization of Nonactivated Alkyl Chlorides

Nonactivated alkyl chlorides are readily available and bench-stable feedstocks; however, they exhibit an inherent chemical inertness, in part, due to their large negative reduction potentials, which have precluded their widespread use as radical precursors in visible-light photocatalysis. Herein, we...

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Detalles Bibliográficos
Autores: Claros, Miguel, Casitas, Alicia, Lloret-Fillol, Julio
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/362327
Acceso en línea:http://hdl.handle.net/2072/362327
https://doi.org/10.1055/s-0037-1611878
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:Nonactivated alkyl chlorides are readily available and bench-stable feedstocks; however, they exhibit an inherent chemical inertness, in part, due to their large negative reduction potentials, which have precluded their widespread use as radical precursors in visible-light photocatalysis. Herein, we highlight some recent strategies for activating challenging organic halides under light irradiation, with special emphasis in C(sp3)–halide bonds. In this line, a brief summary of the reactivity of Vitamin B12, F430 cofactor and derivatives is required to comprehend the chemistry behind our developed Cu/M (M = Co, Ni) dual catalytic system. Catalyst design has been key for developing a mild and general photoredox methodology for the intramolecular reductive cyclization of nonactivated alkyl chlorides with tethered alkenes. The cleavage of strong C(sp3)–Cl bonds is mediated by a highly nucleophilic low-valent cobalt or nickel intermediate generated by visible-light photoredox reduction employing a copper photosensitizer.