Diels-Alder Active-Template Synthesis of Rotaxanes and Metal-Ion-Switchable Molecular Shuttles

James D. Crowley, Kevin D. Haenni, David A. Leigh, Alexandra M. Z. Slawin

Research output: Contribution to journalArticlepeer-review

60 Citations (Scopus)

Abstract

A synthesis of [2]rotaxanes in which Zn(II) or Cu(II) Lewis acids catalyze a Diels-Alder cycloaddition to form the axle while simultaneously acting as the template for the assembly of the interlocked molecules is described. Coordination of the Lewis acid to a multidentate endotopic 2,6-di(methyleneoxy-methyl)pyridyl- or bipyridine-containing macrocycle orients a chelated dienophile through the macrocycle cavity. Lewis acid activation of the double bond causes it to react with an incoming "stoppered" diene, affording the [2]rotaxane in up to 91% yield. Unusually for an active-template synthesis, the metal binding site "lives on" in these rotaxanes. This was exploited in the synthesis of a molecular shuttle containing two different ligating sites in which the position of the macrocycle could be switched by complexation with metal ions [Zn(II) and Pd(II)] with different preferred coordination geometries.

Original languageEnglish
Pages (from-to)5309-5314
Number of pages6
JournalJournal of the American Chemical Society
Volume132
Issue number14
DOIs
Publication statusPublished - 14 Apr 2010

Keywords

  • DIFFERENT COORDINATING UNITS
  • TRANSITION-METAL
  • INTERLOCKED MOLECULES
  • CHIRAL AMPLIFICATION
  • ANION TEMPLATION
  • MECHANICAL BONDS
  • COPPER COMPLEX
  • CATENANES
  • RING
  • CYCLOADDITIONS

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