Autor segons l'article: Echavarren, A.M. ; De Orbe, M.E.; Amenós, L.; Kirillova, M.S. ; Wang, Y.; López-Carrillo, V.; Maseras, F.
Departament: Química Analítica i Química Orgànica
Autor/s de la URV: ECHAVARREN PABLOS, ANTONIO MARIA; De Orbe, M.E.; Amenós, L.; Kirillova, M.S. ; Wang, Y.; López-Carrillo, V.; Maseras, F.
Paraules clau: Gold catalysis
Resum: 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.
Àrees temàtiques: Chemistry Química Química
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0002-7863
Identificador de l'autor: 0000-0001-6808-3007; ; ; ; ; ;
Data d'alta del registre: 2018-02-05
Pàgina final: 10311
Volum de revista: 139
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/abs/10.1021/jacs.7b03005
DOI de l'article: 10.1021/jacs.7b03005
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2017
Pàgina inicial: 10302
Tipus de publicació: Article Artículo Article
Repositori URV