title: Accounting for Diradical Character through DFT. The Case of Vinyl Allene Oxide Rearrangement.
abstract: The transformation of vinyl allene oxides into cyclopentenones is key to the biosynthesis of a number of hormone-like molecules in plants. Two competitive paths are generally accepted for this transformation: a concerted SN2-like mechanism and a stepwise path with a diradical oxyallyl intermediate. Recently, a new stepwise closed-shell path has been proposed that circumvents the key oxyallyl intermediate. In this work, we conduct a thorough computational investigation, including dynamic effects, to identify the most likely mechanism for this transformation.
authors.affiliation: Departamento de Química Orgánica, Campus Lagoas-Marcosende , 36310 Vigo, Spain.
authors.forename: Roberto Villar
authors.initials: RV
authors.lastname: López
authors.affiliation: Departamento de Química Orgánica, Campus Lagoas-Marcosende , 36310 Vigo, Spain.
authors.forename: Olalla Nieto
authors.initials: ON
authors.lastname: Faza
authors.affiliation: Departamento de Química Orgánica, Campus Lagoas-Marcosende , 36310 Vigo, Spain.
authors.forename: Carlos Silva
authors.initials: CS
authors.lastname: López