1. Importance of Off-Cycle Species in the Acid-Catalyzed Aza-Piancatelli Rearrangement
- Author
-
Yu, Diana, Thai, Van T, Palmer, Leoni I, Veits, Gesine K, Cook, Jonathan E, Read de Alaniz, Javier, and Hein, Jason E
- Subjects
Acids ,Aza Compounds ,Catalysis ,Dysprosium ,Molecular Structure ,Medicinal and Biomolecular Chemistry ,Organic Chemistry - 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.
- Published
- 2013