title: Mechanism of the gold-catalyzed rearrangement of (3-acyloxyprop-1-ynyl)oxiranes: a dual role of the catalyst.
abstract: The three competing paths for the rearrangement of 1 (involving 1,2- and 1,3-ester migration with alkyne or oxirane activation) evidence the multifaceted character of gold as a catalyst. The most favorable mechanism for this useful synthetic transformation involves a cascade of more than eight steps. All the functional groups in the substrate play a crucial and synergistic role, and sequential gold coordination to both the pi-system and the lone pairs of oxygen is needed. Exploration of these three paths suggests the use of a nonalkynophilic Lewis acid (BF(3)) as a possible synthetic alternative for this transformation.
authors.affiliation: Departamento de Quimica Organica, Facultade de Quimica, Universidade de Vigo, 36310 As Lagoas-Marcosende s/n, Spain.
authors.forename: Adán
authors.initials: A
authors.lastname: González Pérez
authors.forename: Carlos
authors.initials: C
authors.lastname: Silva López
authors.forename: José
authors.initials: J
authors.lastname: Marco-Contelles
authors.forename: Olalla
authors.initials: O
authors.lastname: Nieto Faza
authors.forename: Elena
authors.initials: E
authors.lastname: Soriano
authors.forename: Angel R
authors.initials: AR
authors.lastname: de Lera