title: Importance of off-cycle species in the acid-catalyzed aza-Piancatelli rearrangement.
abstract: The observed rate of reaction in the dysprosium triflate catalyzed aza-Piancatelli rearrangement is controlled by a key off-cycle binding between aniline and catalyst. Deconvoluting the role of these ancillary species greatly broadens our understanding of factors affecting the productive catalytic pathway. We demonstrate that the rate of reaction is controlled by initial competitive binding between the furylcarbinol and nitrogen nucleophile using either a Brønsted or Lewis acid catalyst and that the resulting rearrangement proceeds without involving the Brønsted and Lewis acid catalyst. This shows conclusively that the rate-controlling step and selectivity of reaction are decoupled.
authors.affiliation: Chemistry and Chemical Biology, University of California , Merced, California 95343, United States.
authors.forename: Diana
authors.initials: D
authors.lastname: Yu
authors.forename: Van T
authors.initials: VT
authors.lastname: Thai
authors.forename: Leoni I
authors.initials: LI
authors.lastname: Palmer
authors.forename: Gesine K
authors.initials: GK
authors.lastname: Veits
authors.forename: Jonathan E
authors.initials: JE
authors.lastname: Cook
authors.forename: Javier Read
authors.initials: JR
authors.lastname: de Alaniz
authors.forename: Jason E
authors.initials: JE
authors.lastname: Hein
mesh_terms: D000143:Acids / Q000737:chemistry*; D001372:Aza Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004419:Dysprosium / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D000143:Acids; D001372:Aza Compounds; D004419:Dysprosium