Enantioselective Copper-Catalysed Azide-Alkyne Cycloaddition Reactions.

Martin, James Patrick (2020) Enantioselective Copper-Catalysed Azide-Alkyne Cycloaddition Reactions. Doctoral thesis, University of East Anglia.

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Abstract

Key Words: Click chemistry, Enantioselective synthesis, Enantioselective desymmetrisation, Kinetic resolution, Copper catalysis, Copper-catalysed azidealkyne Cycloaddition

This thesis describes an investigation into the enantioselective copper-catalysed azide-alkyne cycloaddition reaction as a tool for the synthesis of chiral alkynes and triazoles through the desymmetrisation of prochiral bis(alkynes) and the kinetic resolutions of chiral alkynes.

This thesis will provide an introduction outlining a brief history of the coppercatalysed azide-alkyne cycloaddition reaction followed by an overview of the proposed mechanisms for the reaction. A condensed showcase of the wide range of chemical disciplines the CuAAC reaction has found application in will be provided. Literature examples of enantioenriched chiral triazoles will be discussed across three subchapters, covering synthesis from enantioenriched starting materials, enantioselective desymmetrisations of prochiral triazoles, and finally, the focus of this thesis, synthesis by enantioselective CuAAC reactions.

The research discussed in this thesis is split into four chapters:

The first chapter examines the initial development of an asymmetric screening reaction and details substrate synthesis, solvent screening, and copper(I) source screening.

The second chapter details the screening of chiral ligands, and is further divided into discussion of oxazoline ligands, phosphine ligands, and N-hetrocyclic carbene ligands.

The third chapter discusses the use of ferrocenyl ligands and examines the effect of temperature and in situ kinetic resolutions on the observed enantioselectivity of the asymmetric CuAAC reaction

The fourth chapter describes the scope of substrates investigated.

Item Type: Thesis (Doctoral)
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Chris White
Date Deposited: 25 Aug 2021 09:58
Last Modified: 25 Aug 2021 09:58
URI: https://ueaeprints.uea.ac.uk/id/eprint/81193
DOI:

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