Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.584134
Title: Theoretical investigation into asymmetric iminium ion organocatalysis
Author: Evans, Gareth J. S.
Awarding Body: Cardiff University
Current Institution: Cardiff University
Date of Award: 2007
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Abstract:
The scope of this thesis covered three main areas of this emerging area of chemistry. A reaction pathway is proposed for the formation of iminium ion intermediates from the reaction of secondary amines with carbonyl compounds. This suggests the deprotonation of the amine as the rate-determining step. The effect of modification of amine structure on this pathway was studied, and rationalised using Atoms-in-Molecules analysis. Molecular properties were used to describe a range of secondary amines with an aim to find a relationship between composition and reactivity. A number of catalytic candidates were suggested for synthesis. Two reaction types that directly and indirectly utilise iminium ions as catalysts or intermediates were covered. This included studies of model amines, as well as those in current use as asymmetric catalysts. The Diels-Alder reaction was studied in depth for a number of iminium ions. The alpha-acyloxylation of enamines was also studied, and reaction profiles in gas-phase and solvent identified, and possible mechanisms of asymmetric induction explored.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.584134  DOI: Not available
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