Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles

The opening chapter of this thesis gives an overview of the existing methods to functionalise palladium(II)-alkyl intermediates resulting from oxy- or carbopalladation of unactivated alkenes, outlining the range of heterocycles which can be formed using this type of methodology. A summary of Pd(IV)...

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Main Author: Hewitt, Joanne F. M.
Published: University of Glasgow 2014
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547
Online Access:http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.601592
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spelling ndltd-bl.uk-oai-ethos.bl.uk-6015922016-08-04T03:20:52ZDevelopment of methodology for the palladium-catalysed synthesis of oxygen-containing heterocyclesHewitt, Joanne F. M.2014The opening chapter of this thesis gives an overview of the existing methods to functionalise palladium(II)-alkyl intermediates resulting from oxy- or carbopalladation of unactivated alkenes, outlining the range of heterocycles which can be formed using this type of methodology. A summary of Pd(IV) species in synthesis and catalysis follows, with a focus on Pd(IV) intermediates arising from oxidative addition of alkyl halides to Pd(II) and those suggested in alkene difunctionalisation reactions. As the subsequent formation of sp3–sp3 C–C bonds from Pd(II)-alkyl intermediates was noted as a limitation of prevailing nucleopalladation methods, the second chapter of this thesis outlines the work towards development of an oxypalladation reaction of hydroxyalkenes, with concomitant formation of an sp3–sp3 C–C bond. Allyl halides proved to be competent electrophiles for this transformation. The oxyallylation reaction was successfully applied to a range of hydroxyalkene substrates, with the methodology developed also applied to a 5-step synthesis of anti-depressant citalopram. The oxyallylation reaction constructs heterocycles substituted in the 2-position, forming two new bonds in a single step. Ensuing work, detailed in Chapter 3, focused on the development of an analogous carboallylation reaction, using aryl boronic acid derivatives. This transformation gives rise to the formation of two new C–C bonds in a single step, including the construction of a fully substituted carbon centre. Experimental procedures and data are summarised in Chapter 4.547QD ChemistryUniversity of Glasgowhttp://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.601592http://theses.gla.ac.uk/5096/Electronic Thesis or Dissertation
collection NDLTD
sources NDLTD
topic 547
QD Chemistry
spellingShingle 547
QD Chemistry
Hewitt, Joanne F. M.
Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
description The opening chapter of this thesis gives an overview of the existing methods to functionalise palladium(II)-alkyl intermediates resulting from oxy- or carbopalladation of unactivated alkenes, outlining the range of heterocycles which can be formed using this type of methodology. A summary of Pd(IV) species in synthesis and catalysis follows, with a focus on Pd(IV) intermediates arising from oxidative addition of alkyl halides to Pd(II) and those suggested in alkene difunctionalisation reactions. As the subsequent formation of sp3–sp3 C–C bonds from Pd(II)-alkyl intermediates was noted as a limitation of prevailing nucleopalladation methods, the second chapter of this thesis outlines the work towards development of an oxypalladation reaction of hydroxyalkenes, with concomitant formation of an sp3–sp3 C–C bond. Allyl halides proved to be competent electrophiles for this transformation. The oxyallylation reaction was successfully applied to a range of hydroxyalkene substrates, with the methodology developed also applied to a 5-step synthesis of anti-depressant citalopram. The oxyallylation reaction constructs heterocycles substituted in the 2-position, forming two new bonds in a single step. Ensuing work, detailed in Chapter 3, focused on the development of an analogous carboallylation reaction, using aryl boronic acid derivatives. This transformation gives rise to the formation of two new C–C bonds in a single step, including the construction of a fully substituted carbon centre. Experimental procedures and data are summarised in Chapter 4.
author Hewitt, Joanne F. M.
author_facet Hewitt, Joanne F. M.
author_sort Hewitt, Joanne F. M.
title Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
title_short Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
title_full Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
title_fullStr Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
title_full_unstemmed Development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
title_sort development of methodology for the palladium-catalysed synthesis of oxygen-containing heterocycles
publisher University of Glasgow
publishDate 2014
url http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.601592
work_keys_str_mv AT hewittjoannefm developmentofmethodologyforthepalladiumcatalysedsynthesisofoxygencontainingheterocycles
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