Autor según el artículo: Echavarren, A.M. ; De Orbe, M.E.; Amenós, L.; Kirillova, M.S. ; Wang, Y.; López-Carrillo, V.; Maseras, F.

Departamento: Química Analítica i Química Orgànica

Autor/es de la URV: ECHAVARREN PABLOS, ANTONIO MARIA; De Orbe, M.E.; Amenós, L.; Kirillova, M.S. ; Wang, Y.; López-Carrillo, V.; Maseras, F.

Palabras clave: Gold catalysis

Resumen: The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type process. The corresponding reaction of alkenes with aryl-1,3-butadiynes, ethynylogous to arylalkynes, leads exclusively to cyclobutenes. A comprehensive mechanism for the gold(I)-catalyzed reaction of alkynes with alkenes is proposed on the basis of density functional theory calculations, which shows that the two pathways leading to cyclobutenes or dienes are very close in energy. The key intermediates are cyclopropyl gold(I) carbenes, which have been independently generated by retro-Buchner reaction from stereodefined 1a,7b-dihydro-1H-cyclopropa[a]naphthalenes.

Áreas temáticas: Chemistry Química Química

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 0002-7863

Identificador del autor: 0000-0001-6808-3007; ; ; ; ; ;

Fecha de alta del registro: 2018-02-05

Página final: 10311

Volumen de revista: 139

Versión del articulo depositado: info:eu-repo/semantics/publishedVersion

Enlace a la fuente original: https://pubs.acs.org/doi/abs/10.1021/jacs.7b03005

DOI del artículo: 10.1021/jacs.7b03005

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2017

Página inicial: 10302

Tipo de publicación: Article Artículo Article