title: Mechanistic studies on the rearrangement of 1-alkenyl-2-alkynylcyclopropanes: from allylic gold(I) cations to stable carbocations.
abstract: An allylic gold(I) cation, proposed as key intermediate in the gold-promoted rearrangement of 1,5-enynes bearing a fixed conformation, has been detected and characterized by NMR spectroscopy. Moreover, its participation in the overall transformation was confirmed. Computational studies indicate that the gold-catalyzed transformation occurs through an uncommon rearrangement. Additionally, this study led us to isolate and characterize a stable homoantiaromatic carbocation.
authors.affiliation: Instituto de Química Organometálica "Enrique Moles" and Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, c/Julián Clavería 8, 33007, Oviedo (Spain).
authors.forename: Eva
authors.initials: E
authors.lastname: Tudela
authors.forename: Jairo
authors.initials: J
authors.lastname: González
authors.forename: Rubén
authors.initials: R
authors.lastname: Vicente
authors.forename: Javier
authors.initials: J
authors.lastname: Santamaría
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Rodríguez
authors.forename: Alfredo
authors.initials: A
authors.lastname: Ballesteros
keywords: allylic compounds; carbocations; gold; reactive intermediates; rearrangements