title: Truce-Smiles rearrangement of substituted phenyl ethers.
abstract: The requirement of aryl ring activation by strong-electron withdrawing substituents in substrates for the intramolecular nucleophilic aromatic substitution reaction known as the Truce-Smiles rearrangement was examined. Preliminary mechanistic experiments support the SNAr mechanism, including (1)H and (13)C NMR spectra of a Meisenheimer intermediate formed in situ. The rearrangement was generally observed to be successful for substrates with strong electron withdrawing substituents, such as nitro-, cyano-, and benzoyl- functional groups, but also for those with multiple, weakly electron withdrawing substituents, such as chloro- and bromo-functional groups. These results lend further clarification to the effect of aryl substituents in this type of SNAr reaction. Additionally, the survey revealed several tandem cyclization and/or elimination reactions accessed by certain substrates.
authors.affiliation: Department of Chemistry, The University of Winnipeg, 515 Portage Avenue, Winnipeg, Manitoba, CanadaR3B 2E9. te.wood@uwinnipeg.ca.
authors.forename: Joel R
authors.initials: JR
authors.lastname: Kosowan
authors.forename: Zemane
authors.initials: Z
authors.lastname: W'Giorgis
authors.forename: Ravneet
authors.initials: R
authors.lastname: Grewal
authors.forename: Tabitha E
authors.initials: TE
authors.lastname: Wood