Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction

The most useful strategies for the alkylation of allylic systems are related to the Tsuji–Trost reaction or the use of different Lewis acids. Herein we report a photocatalytic approach for the allylation reaction of a variety of nucleophiles, such as heteroarenes, amines and alcohols. This method is...

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Detalles Bibliográficos
Autores: Martínez-Gualda, Ana María, Cano, Rafael, Marzo, Leyre, Pérez-Ruiz, Raúl, Luis Barrera, Javier, Mas Ballesté, Rubén, Fraile Carrasco, Alberto, Peña O'Shea, Victor Antonio de la, Alemán Lara, José Julián
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/690874
Acceso en línea:http://hdl.handle.net/10486/690874
https://dx.doi.org/10.1038/s41467-019-10441-4
Access Level:acceso abierto
Palabra clave:Alkylation of allylic systems
Tsuji–Trost reaction
Chromoselective synthesis
Química
Descripción
Sumario:The most useful strategies for the alkylation of allylic systems are related to the Tsuji–Trost reaction or the use of different Lewis acids. Herein we report a photocatalytic approach for the allylation reaction of a variety of nucleophiles, such as heteroarenes, amines and alcohols. This method is compatible with a large variety of pyrroles and indoles, containing different substituents such as electron-withdrawing and electron-donating groups, unprotected nitrogen atoms and bromo derivatives. Moreover, this methodology enables the chromoselective synthesis of Z- or E-allylated compounds. While the use of UV-light irradiation has allowed the synthesis of the previously inaccessible Z-allylated products, E-isomers are prepared simply by changing both the light source to the visible region, and the catalytic system. Based on mechanistic and photochemical proofs, laser flash photolysis studies and DFT calculations, a rational mechanism is presented