The Hitchhiker's Guide to Mechanical Stereochemistry

Abstract

Since the earliest report of their discussion over a century ago, interlocked molecular structures have developed from theoretical oddities to readily accessible structures. While the apparent synthetic challenge they originally presented has since been overcome thanks to the development of template approaches, the understanding of stereochemistry that can arise in such systems remained vague until recently.
The first chapter of this thesis introduces the concept and consequences of mechanical bonding, followed by discussion of both how language to describe, and strategies to prepare mechanically interlocked molecules have developed. The stereochemistry that can arise in interlocked molecules is then discussed in detail, as well as advances in the selective synthesis of mechanically stereogenic molecules. The second chapter describes the synthesis of mechanically axially chiral catenanes by a co-conformational auxiliary strategy and also the identification and synthesis of a rotaxane bearing the analogous stereogenic unit. The third chapter describes the investigation into how facial selectivity can arise in mechanical bond formation towards mechanically axially chiral rotaxanes and mechanical geometric isomers. Their diastereoselective synthesis was optimised and was able to be extended to the direct enantioselective synthesis of a mechanically axially chiral rotaxane. Finally, the fourth chapter describes the diastereoselective synthesis of rotaxanes containing a previously overlooked form of mechanical geometric isomerism and also analyses stereochemistry in rotaxanes and catenanes to establish that this is the final mechanical stereogenic unit to be identified.

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Identifiers

ORCID for Peter Gallagher: orcid.org/0000-0002-5501-523X

ORCID for Stephen Goldup: orcid.org/0000-0003-3781-0464

ORCID for Sam Thompson: orcid.org/0000-0001-6267-5693

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