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Novel calcium complexes applied to intramolecular hydroamination catalysis

Wixey, James S. 2012. Novel calcium complexes applied to intramolecular hydroamination catalysis. PhD Thesis, Cardiff University.
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Abstract

This thesis discusses the synthesis, characterisation, and reactivity studies of a range of new chiral calcium complexes supported by various polydentate N-donor ligands and their suitability as catalysts for intramolecular hydroamination. Chapter One outlines the case for developing organocalcium complexes, including a general overview of their current application to a variety of heterofunctionalisation reactions. Chapter Two introduces the chiral ethylene diamines which are extensively used as calcium supporting ligands and later as precursors for the synthesis of bisimidazoline and potential imoxazoline ligands. Chapter Two provides details of the diamine synthesis and includes studies related to racemisation concerns of the chiral centre. Chapter Three discusses novel calcium complexes supported by the chiral ethylene diamine analogues presented in Chapter Two. Complex synthesis, characterisation, and catalytic performance in intramolecular hydroamination is probed and discussed. Chapter Four details a range of new bisimidazoline ligands and their employment as supporting ligands on calcium. The catalytic performance of the resulting complexes in intramolecular hydroamination is subsequently analysed and discussed. Chapter Five investigates the attempted development of a total synthetic pathway to a new class of imoxazoline ligand and related issues. Chapter Six contains all experimental procedures, characterising data pertaining to all new compounds and complexes presented in this Thesis. Appendices A-K contain additional catalytic figures and tables of crystallographic data for all new crystallographically characterised compounds. Summary sheets of every literature and new compound presented mentioned in this Thesis are also included, along with copies of both printed publications resulting from this Thesis at the time of submission.

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Funders: EPSRC, Leverhulme Trust
Date of First Compliant Deposit: 30 March 2016
Last Modified: 19 Mar 2016 23:05
URI: https://orca.cardiff.ac.uk/id/eprint/37858

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