Novel calcium complexes applied to intramolecular hydroamination catalysis
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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