title: Apparent alkyl transfer and phenazine formation via an aryne intermediate.
abstract: Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triazaorthocyclophane 2a. The phenazine derivatives were isolated in 78-98% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via the intermediacy of the aryne intermediate. Mechanistic possibilities include intramolecular nucleophilic attack on an aryne intermediate leading to a zwitterionic intermediate and alkyl transfer via a 5-endo-tet process, or via a Smiles rearrangement.
authors.affiliation: Department of Chemistry, Loyola University Chicago, 1032 West Sheridan Road, Chicago, Illinois 60660, USA.
authors.forename: Andria M
authors.initials: AM
authors.lastname: Panagopoulos
authors.forename: Doug
authors.initials: D
authors.lastname: Steinman
authors.forename: Alexandra
authors.initials: A
authors.lastname: Goncharenko
authors.forename: Kyle
authors.initials: K
authors.lastname: Geary
authors.forename: Carlene
authors.initials: C
authors.lastname: Schleisman
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Spaargaren
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.forename: Daniel P
authors.initials: DP
authors.lastname: Becker