Switching Between Anion-Binding Catalysis and Aminocatalysis with a Rotaxane Dual-Function Catalyst

Research output: Contribution to journalArticle

  • External authors:
  • Katarzyna Eichstaedt
  • Javier Jaramillo Garca
  • Vanesa Marcos Algaba
  • Simone Pisano
  • Thomas Singleton

Abstract

The ‘off’ state for aminocatalysis by a switchable [2]rotaxane is shown to correspond to an ‘on’ state for anion-binding catalysis. Conversely, the aminocatalysis ‘on’ state of the dual-function rotaxane is inactive in anion-binding catalysis. Switching between the different states is achieved through the stimuli-induced change of position of the macrocycle on the rotaxane thread. The anion-binding catalysis results from a pair of triazolium groups that act together to CH-hydrogen bond to halide anions when the macrocycle is located on an alternative (ammonium) binding site, stabilizing the in situ generation of benzhydril cation and oxonium ion intermediates from activated alkyl halides. The aminocatalysis and anion-binding catalysis sites of the dual-function rotaxane catalyst can be sequentially concealed or revealed, enabling catalysis of both steps of a tandem reaction process.

Bibliographical metadata

Original languageEnglish
JournalJournal of the American Chemical Society
Early online date19 Jun 2017
DOIs
Publication statusPublished - 2017

Related information

Researchers

View all