Apparent alkyl transfer and phenazine formation via an aryne intermediate.

TitleApparent alkyl transfer and phenazine formation via an aryne intermediate.
Publication TypeJournal Article
Year of Publication2013
AuthorsPanagopoulos AM, Steinman D, Goncharenko A, Geary K, Schleisman C, Spaargaren E, Zeller M, Becker DP
JournalThe Journal of organic chemistry
Volume78
Issue8
Pagination3532-40
Date Published2013 Apr 19
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.

DOI10.1371/journal.pone.0077060
Alternate JournalJ. Org. Chem.