The research described in this thesis is concerned with the exploitation of a nonracemic chiral base to create enantiomerically enriched chiral centres on the benzylic positions of arene chromium tricarbonyl complexes. The first chapter is in two parts. The first part contains a historical overview of chiral bases and their use in asymmetric synthesis, as well as demonstrating the versatility of chiral base reactions. The latter part deals with the chemistry of arene chromium tricarbonyl complexes and how these molecules have been used in asymmetric synthesis and as ligands in asymmetric catalysis. The second chapter looks at the synthesis of a novel benzyl phosphine chromium tricarbonyl complex and attempts to asymmetrically deprotonate the molecule in order to create a new chiral monophosphine. The third chapter describes the generation of a range of novel monophosphine ligands, based on an arene chromium tricarbonyl core, by exploitation of an asymmetric deprotonationlelectrophilic quench sequence. the novel monophosphines have been assayed in the asymmetric hydrosilylation reaction, and the results are presented and discussed. The fourth chapter is a study of arene chromium tricarbonyl complexes of dibenzyl ethCl and a dibclIzy laminc, dnd their as) mmetr ie dept otonatiol'l. The genet [tHon of new C2-symmetric ethers with high enantioselectivity is demonstrated. The fifth chapter describes the attempted construction of a novel chiral C3-symmetric triol using the chiral base mediated asymmetric benzylic functionalisation approach. The sixth chapter contains the experimental details of the work presented in Chapters two, three, four and five. Chapter seven provides the bibliographic information.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:504763 |
| Date | January 2007 |
| Creators | Rooney, Aaron |
| Publisher | Imperial College London |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/10044/1/11891 |
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