Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols

Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields and enantioselecti...

Descripción completa

Detalles Bibliográficos
Autores: Salaverri Mora, Noelia, Carli, Benedetta, Díaz-Tendero Victoria, Sergio, Marzo Puerta, Leyre, Alemán Lara, José Julián
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/703089
Acceso en línea:http://hdl.handle.net/10486/703089
https://dx.doi.org/10.1021/acs.orglett.2c00662
Access Level:acceso abierto
Palabra clave:Química
Descripción
Sumario:Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields and enantioselectivites up to 99% are achieved in 1 h. Mechanistic investigations support the formation of the remote alkyl radical by a PCET process, and theoretical studies explain the observed stereochemistry in the addition step