Copy of author's previously published article inserted. / Bibliography: leaves 192-197. / iv, 197 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / The pheromone (+)-grandisol was synthesized. Optical activity was induced in the primary alcohol by a kinetic resolution reaction which involved the Sharpless asymmetric epoxidation reaction. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemistry, 1999

Thesis (MScIng)--University of Stellenbosch, 2006. / Bibliography.

Thesis (M. Sc.)--University of Adelaide, Dept. of Chemistry, 1999. / Includes bibliographical references (leaves 100-102).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1952. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record.

Copy of author's previously published article inserted. Bibliography: leaves 192-197. The pheromone (+)-grandisol was synthesized. Optical activity was induced in the primary alcohol by a kinetic resolution reaction which involved the Sharpless asymmetric epoxidation reaction.

This thesis describes the study of organozirconium reagents used in copper-catalyzed asymmetric synthesis. Explorations on the asymmetric allylic alkylation of linear substrates, the cyclic substrates and enantioselective desymmetrization of meso compounds including the oxabicyclic alkenes and meso-allyl substrates are reported here. <strong>Chapter 1</strong> has a brief overview about general methods used in asymmetric catalysis. In particular, more relevant introduction about catalytic asymmetric allylic substitution and asymmetric desymmetrization of meso compounds is given. <strong>Chapter 2</strong> describes the investigation of organozirconium reagents used in copper-catalyzed asymmetric allylic alkylation of linear substrates, and discloses a dynamic kinetic AAA system that employs cyclic allylic chlorides as substrates. <strong>Chapter 3</strong> presents the study on expanding the disclosed copper-catalyzed dynamic kinetic AAA chemistry by using more stabilized cyclic allylic phosphate substrates. Further exploration of its possible mechanisms uses substituted substrates, deuterated and enantiopure substrates are also discussed. <strong>Chapter 4</strong> demonstrates the study of organozirconium reagents used in copper-catalyzed enantioselective desymmetrization reactions. Investigation of oxabicyclic alkenes and mesoallyl substrates is reported. <strong>Chapter 5</strong> gives supporting information of this thesis.

Cycloparaphenylenes (CPPs) represent the unit-cycles of conductive armchair carbon nanotubes (CNTs). In addition to their utility for the bottom-up synthesis of CNTs with discrete diameter and chirality, these strained hydrocarbon macrocycles have attractive properties of their own for material science and organic electronics. Herein I report research focused on advancing the synthetic technology behind CPPs, culminating in the synthesis of [5]CPP, the smallest and most highly-strained member of the CPP series to date, as well as the derivitization of the CPP platform to include chiral nanohoops with a spiral carbon backbone and photoswitchable nanohoops based on azobenzene incorporation into the CPP architecture. The synthesis and characterization of [5]CPP, 1,5-naphthyl[6]CPP, azo[11]CPP, and azo[9]CPP are reported along with advanced intermediates towards rotationally restricted 2,6-naphthyl[6]CPP and preliminary photoisomerization results for azo[11]CPP and azo[9]CPP. This dissertation contains both previously published and unpublished co-authored material.

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D.Sc. (Chemistry) / Please refer to full text to view abstract

This thesis is divided into three sections. The first section of the thesis includes the synthesis and characterization of a catechol-containing [2]pseudorotaxane which established a model for pseudorotaxane formation prepared through slippage method. The pseudorotaxane formation is performed in different solvents at elevated temperature in a period of time and the progress of pseudorotaxane formations were monitored with 1H NMR spectroscopy. The [2]pseudorotaxane had been successfully synthesized in acetonitrile (MeCN) at 60 oC for 5 d with 29% yield. The second section of the thesis demonstrates the potential of the [1]pseudorotaxane to work as a nanovalve. The opening of valve had been investigated and quantified in the presence of external stimuli such as heat, ultrasound, pH and alternating magnetic field (AMF). Furthermore, a novel core-satellite Fe3O4 nanocomposite had been prepared for AMF responsive controlled drug released system. The cytotoxicity of the core-satellite Fe3O4 nanocomposite had also been investigated and quantified in human gingival epithelial cells and human epithelial cell line, FaDu, from a squamous cell carcinoma of the hypopharynx. The core-satellite Fe3O4 nanocomposite showed non-cytotoxicity at concentration lower than 200 μg/mL and 100 μg/mL towards HGEPs and FaDu respectively. The third section of the thesis illustrates the synthesis of a novel [1]pseudorotaxane from a signal compound which consists of a macrocycle and a coordination site through a slippage approach. The formation of mechanically interlocked molecules restricted the twisted intramolecular charge transfer (TICT) quenching process and an enhancement of fluorescence intensity was observed. With a potential to act as a fluorescent probe, the fluorescence and fluorescence-quenching nature of the [1]pseudorotaxane had been investigated and quantified in the presence of external stimuli such as base, acid and salt. Furthermore, a series of cations and anions had been screened. The results suggested that the [1]pseudorotaxane was a highly selective phosphate ion sensor and working with a linear operating mode.