Rotaxane synthesis via the 'threading followed by stoppering' approach

Doctoral thesis English OPEN
Yates, Jennifer
  • Subject: QD

The development of template directed synthesis towards the formation of interlocked\ud architectures has allowed for the synthesis of a variety of rotaxanes. Chapter 1 covers the\ud history of rotaxanes including their nomenclature and methods of formation. An overview of\ud the intermolecular interactions used to facilitate the synthesis of these architectures is\ud described and examples of template directed synthesis and properties of rotaxanes are\ud discussed.\ud In Chapter 2 the use of the Diels-Alder reaction towards formation of rotaxanes in a\ud ‘threading followed by stoppering’ protocol is covered. The synthesis of [n]rotaxanes is\ud described with secondary ammonium ions, a novel perimidine benzimidazole and\ud bispyridinium binding templates integrated into threads.\ud In Chapter 3 a novel binding template was developed, incorporating a triazole into a\ud dibenzylammonium binding motif. Binding studies were carried out and [n]rotaxanes were\ud synthesised using this motif with the groups Diels-Alder ‘threading followed by stoppering’\ud protocol.\ud Chapter 4 discusses the modification of the DB24C8 macrocycle with the aim to enhance\ud binding interactions with a variety of binding motifs. Two macrocycles were successfully\ud synthesised and their binding affinities calculated with known and novel binding templates\ud investigated in the previous chapters.\ud The work in this thesis shows a Diels-Alder stoppering reaction can be successfully used to\ud synthesise [n]rotaxanes with a variety of binding templates including novel templates\ud discovered during this project. During the work it was also revealed that modifications to\ud known binding templates can provide an enhancement in binding interactions in comparison\ud to their unmodified predecessors.
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