title: A forbidden rearrangement.
abstract: [reaction: see text] A barrelene derivative fragments to afford benzene and trappable 1,2,3-tricyanocyclopropene. The barrelene anion fragments more easily to liberate benzene and the 1,2,3-tricyanocyclopropenyl anion, which is not trappable or stable in solution. However, the major thermal product from the barrelene anion is a rearranged allyl anion that is formed by disrotatory cleavage of the cyclopropyl ring, a formally Woodward-Hoffmann-forbidden process. Several proposals are offered to rationalize this forbidden rearrangement.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: Martin
authors.initials: M
authors.lastname: Leivers
authors.forename: Iris
authors.initials: I
authors.lastname: Tam
authors.forename: Kevin
authors.initials: K
authors.lastname: Groves
authors.forename: David
authors.initials: D
authors.lastname: Leung
authors.forename: Yuli
authors.initials: Y
authors.lastname: Xie
authors.forename: Ronald
authors.initials: R
authors.lastname: Breslow