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Consequences of the mechanical bond in rotaxanes; novel reactivity and unusual chirality

Consequences of the mechanical bond in rotaxanes; novel reactivity and unusual chirality
Consequences of the mechanical bond in rotaxanes; novel reactivity and unusual chirality
Reports of mechanically interlocked molecules (MIMs) have grown in recent years, aided by the relative synthetic ease by which they can now be obtained in comparison to the challenging syntheses reported originally. With this influx of research into the area, boosted even more by the 2016 Nobel Prize in the field for ‘the design and production of molecular machines’ there have been a lot of recent developments, showing the potential of MIMs for different applications such as switches, sensors or in catalysis due to the unique environment of the mechanical bond.

The introductory chapter provides a detailed overview of chirality in the context of MIMs. In addition to discussing the properties and applications of MIMs containing covalent stereogenic units, the different forms of chirality that arise as a consequence of the mechanical bond, and the influence this can have on the properties of molecules will be outlined.

Chapter two details the design and synthesis of a dynamic co-conformationally mechanically planar chiral rotaxane which exists as a pair of rapidly exchanging enantiomers. This novel rotaxane binds diastereoselectively to chiral anions. The biasing of the coconformations of the rotaxane host through guest binding leads to an induced circular dichroism (CD) signal even when the chiral anionic guest does not display a CD signal on its own. Our results demonstrate the long-term potential of such stereodynamic rotaxanes in determining the enantiopurity of chiral analytes.

Chapter three describes the unexpected discovery of a novel acrylamide rotaxane, formed as an unintended consequence of the mechanical bond stabilizing a CuI-triazolide intermediate. This novel reactivity was investigated in depth, firstly by exploring the scope of the reaction and then via experiments designed to gain insight into key reaction intermediates. Using our results, a possible a mechanism of the reaction was proposed.
University of Southampton
Jamieson, Ellen M.G.
34fb77f9-486a-4cae-99b5-5e4fcdf25fe6
Jamieson, Ellen M.G.
34fb77f9-486a-4cae-99b5-5e4fcdf25fe6
Goldup, Stephen
0a93eedd-98bb-42c1-a963-e2815665e937

Jamieson, Ellen M.G. (2020) Consequences of the mechanical bond in rotaxanes; novel reactivity and unusual chirality. University of Southampton, Doctoral Thesis, 270pp.

Record type: Thesis (Doctoral)

Abstract

Reports of mechanically interlocked molecules (MIMs) have grown in recent years, aided by the relative synthetic ease by which they can now be obtained in comparison to the challenging syntheses reported originally. With this influx of research into the area, boosted even more by the 2016 Nobel Prize in the field for ‘the design and production of molecular machines’ there have been a lot of recent developments, showing the potential of MIMs for different applications such as switches, sensors or in catalysis due to the unique environment of the mechanical bond.

The introductory chapter provides a detailed overview of chirality in the context of MIMs. In addition to discussing the properties and applications of MIMs containing covalent stereogenic units, the different forms of chirality that arise as a consequence of the mechanical bond, and the influence this can have on the properties of molecules will be outlined.

Chapter two details the design and synthesis of a dynamic co-conformationally mechanically planar chiral rotaxane which exists as a pair of rapidly exchanging enantiomers. This novel rotaxane binds diastereoselectively to chiral anions. The biasing of the coconformations of the rotaxane host through guest binding leads to an induced circular dichroism (CD) signal even when the chiral anionic guest does not display a CD signal on its own. Our results demonstrate the long-term potential of such stereodynamic rotaxanes in determining the enantiopurity of chiral analytes.

Chapter three describes the unexpected discovery of a novel acrylamide rotaxane, formed as an unintended consequence of the mechanical bond stabilizing a CuI-triazolide intermediate. This novel reactivity was investigated in depth, firstly by exploring the scope of the reaction and then via experiments designed to gain insight into key reaction intermediates. Using our results, a possible a mechanism of the reaction was proposed.

Text
Consequences of the Mechanical Bond in Rotaxanes; Novel Reactivity and Unusual Chirality - Version of Record
Restricted to Repository staff only until 18 December 2022.
Available under License University of Southampton Thesis Licence.

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Published date: January 2020

Identifiers

Local EPrints ID: 439302
URI: http://eprints.soton.ac.uk/id/eprint/439302
PURE UUID: d226f86d-7f70-4d05-9df0-424a1e45256d
ORCID for Stephen Goldup: ORCID iD orcid.org/0000-0003-3781-0464

Catalogue record

Date deposited: 08 Apr 2020 16:30
Last modified: 13 Dec 2021 03:14

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Contributors

Author: Ellen M.G. Jamieson
Thesis advisor: Stephen Goldup ORCID iD

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