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The synthesis and application of novel chiral transition metal complexes

The synthesis and application of novel chiral transition metal complexes
The synthesis and application of novel chiral transition metal complexes

The synthesis of a variety of novel chiral annulated cyclopentadienyl ligands and the preparation of novel chiral metallocene complexes of zirconium, titanium and rhodium is described. The novel complexes are evaluated as catalysts in asymmetric reductions and carbon-carbon bond-forming reactions. Chapter 1 provides an introduction to the research, outlining the methodology and stating the aims of the project. A literature review of chiral annulated cyclopentadienyl ligands and of the use of Group IV metallocenes in asymmetric catalysis is presented. Chapter 2 deals with the synthesis of Group IV metallocenes derived from camphor. Chapter 3 introduces the use of a double-Michael addition reaction to access a variety of elaborate chiral (but racemic) cyclopentadienyl ligands, and their diastereoselective complexation to titanium and zirconium is investigated. In Chapter 4 an enantioselective double-Michael addition reaction is developed, to provide a novel cyclopentadienyl ligand derived from carvone. Titanium and zirconium complexes of the carvone-derived cyclopentadienyl ligand are prepared, and the resulting metallocenes are evaluated in asymmetric catalysis. Chapter 5 describes the synthesis of novel rhodium cyclopentadienyl complexes and their application to catalytic asymmetric hydrogenations. Full experimental details are given in Chapter 6, including complete characterisation of all novel compounds.

University of Southampton
Green, Simon Michael
Green, Simon Michael

Green, Simon Michael (1999) The synthesis and application of novel chiral transition metal complexes. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The synthesis of a variety of novel chiral annulated cyclopentadienyl ligands and the preparation of novel chiral metallocene complexes of zirconium, titanium and rhodium is described. The novel complexes are evaluated as catalysts in asymmetric reductions and carbon-carbon bond-forming reactions. Chapter 1 provides an introduction to the research, outlining the methodology and stating the aims of the project. A literature review of chiral annulated cyclopentadienyl ligands and of the use of Group IV metallocenes in asymmetric catalysis is presented. Chapter 2 deals with the synthesis of Group IV metallocenes derived from camphor. Chapter 3 introduces the use of a double-Michael addition reaction to access a variety of elaborate chiral (but racemic) cyclopentadienyl ligands, and their diastereoselective complexation to titanium and zirconium is investigated. In Chapter 4 an enantioselective double-Michael addition reaction is developed, to provide a novel cyclopentadienyl ligand derived from carvone. Titanium and zirconium complexes of the carvone-derived cyclopentadienyl ligand are prepared, and the resulting metallocenes are evaluated in asymmetric catalysis. Chapter 5 describes the synthesis of novel rhodium cyclopentadienyl complexes and their application to catalytic asymmetric hydrogenations. Full experimental details are given in Chapter 6, including complete characterisation of all novel compounds.

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Published date: 1999

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Local EPrints ID: 463582
URI: http://eprints.soton.ac.uk/id/eprint/463582
PURE UUID: e978bd22-a70f-45ba-bb50-2780e944d795

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Date deposited: 04 Jul 2022 20:54
Last modified: 04 Jul 2022 20:54

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Author: Simon Michael Green

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