title: Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer.
abstract: Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones.
authors.affiliation: Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ (UK).
authors.forename: Théo P
authors.initials: TP
authors.lastname: Gonçalves
authors.forename: Mubina
authors.initials: M
authors.lastname: Mohamed
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Whitby
authors.forename: Helen F
authors.initials: HF
authors.lastname: Sneddon
authors.forename: David C
authors.initials: DC
authors.lastname: Harrowven
keywords: density functional calculations; flow chemistry; radicals; rearrangements; small ring systems