Author, as appears in the article.: Echavarren, A.M. ; De Orbe, M.E.; Amenós, L.; Kirillova, M.S. ; Wang, Y.; López-Carrillo, V.; Maseras, F.
Department: Química Analítica i Química Orgànica
URV's Author/s: ECHAVARREN PABLOS, ANTONIO MARIA; De Orbe, M.E.; Amenós, L.; Kirillova, M.S. ; Wang, Y.; López-Carrillo, V.; Maseras, F.
Keywords: Gold catalysis
Abstract: 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.
Thematic Areas: Chemistry Química Química
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0002-7863
Author identifier: 0000-0001-6808-3007; ; ; ; ; ;
Record's date: 2018-02-05
Last page: 10311
Journal volume: 139
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/abs/10.1021/jacs.7b03005
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1021/jacs.7b03005
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
First page: 10302
Publication Type: Article Artículo Article
Repositori URV