Theoretical investigation into asymmetric iminium ion organocatalysis
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...
Main Author: | |
---|---|
Published: |
Cardiff University
2007
|
Subjects: | |
Online Access: | http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.584134 |
id |
ndltd-bl.uk-oai-ethos.bl.uk-584134 |
---|---|
record_format |
oai_dc |
spelling |
ndltd-bl.uk-oai-ethos.bl.uk-5841342015-03-20T03:21:53ZTheoretical investigation into asymmetric iminium ion organocatalysisEvans, Gareth J. S.2007The 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.541.39Cardiff Universityhttp://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.584134http://orca.cf.ac.uk/55527/Electronic Thesis or Dissertation |
collection |
NDLTD |
sources |
NDLTD |
topic |
541.39 |
spellingShingle |
541.39 Evans, Gareth J. S. Theoretical investigation into asymmetric iminium ion organocatalysis |
description |
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. |
author |
Evans, Gareth J. S. |
author_facet |
Evans, Gareth J. S. |
author_sort |
Evans, Gareth J. S. |
title |
Theoretical investigation into asymmetric iminium ion organocatalysis |
title_short |
Theoretical investigation into asymmetric iminium ion organocatalysis |
title_full |
Theoretical investigation into asymmetric iminium ion organocatalysis |
title_fullStr |
Theoretical investigation into asymmetric iminium ion organocatalysis |
title_full_unstemmed |
Theoretical investigation into asymmetric iminium ion organocatalysis |
title_sort |
theoretical investigation into asymmetric iminium ion organocatalysis |
publisher |
Cardiff University |
publishDate |
2007 |
url |
http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.584134 |
work_keys_str_mv |
AT evansgarethjs theoreticalinvestigationintoasymmetriciminiumionorganocatalysis |
_version_ |
1716780384354566144 |