Thesis (M.S.)--University of Florida, 2006. / Title from title page of source document. Document formatted into pages; contains 68 pages. Includes vita. Includes bibliographical references.

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

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.

Pericyclic reactions are a class of transformations that comprise sigmatropic rearrangements, group transfer reactions, cycloadditions and electrocyclic reactions. Since Woodward and Hoffmann rationalized the mechanism and stereochemistry of pericyclic reactions they have become powerful synthetic tools. Whilst sigmatropic rearrangements and cycloadditions are cornerstones of contemporary synthetic methodology, many electrocyclic reactions are not fully exploited currently; there are no general methods for the asymmetric catalysis of electrocyclic reactions and as a consequence, opportunities for exerting stereocontrol in these manifolds are limited. We aim to establish general methods for the asymmetric catalysis of 6π electrocyclic reactions. Our initial studies are focused on a pentadienyl anion moiety due to the greater ease of cyclization observed with such systems in comparison to the corresponding neutral hexatriene systems.

No description available.

No description available.

No description available.

No description available.

No description available.

No description available.