Gold-catalysed reactions of Nitrogen containing molecules
The development of several new gold-catalysed reactions are described. Two new strategies have been employed to access pyrroles by the cycloisomerisation of alkynyl aziridines, and the formation of α,β-unsaturated imides by the oxidation of ynamides has been developed. A rare gold-mediated vinyliden...
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ndltd-bl.uk-oai-ethos.bl.uk-5248822019-04-03T06:43:24ZGold-catalysed reactions of Nitrogen containing moleculesMartin, Nicolas2010The development of several new gold-catalysed reactions are described. Two new strategies have been employed to access pyrroles by the cycloisomerisation of alkynyl aziridines, and the formation of α,β-unsaturated imides by the oxidation of ynamides has been developed. A rare gold-mediated vinylidene rearrangement of brominated or silylated alkynes has been used to prepare brominated or silylated 2,4-substituted pyrroles regioselectively. The practical applicability of this process was limited by instability of products under the reaction conditions. Cationic gold catalysis was used in a synthesis of 2,4- and 2,5-substituted pyrroles from alkynyl aziridines. The role of counterion in these processes was studied and shown to be important in determining reaction outcomes. A Ph\(_3\)PAuCl/AgOTs catalyst system, allows 2,5-substituted pyrroles to be regioselectively synthesised in an atom-economical manner in near quantitative yield. From the same aryl-substituted starting materials the 2,4-substituted pyrrole isomer were accessed preferentially when a Ph\(_3\)PAuCl/AgOTf catalytic system was employed. A reaction mechanism accounting for the reaction outcome was proposed on the basis of \({^13}\)C- and deuterium-labelling studies. A new gold-catalysed synthesis of α,β-unsaturated imides was developed using a ynamide oxidation approach. Gold carbenoid intermediates can be formed regioselectively by action of an external oxidising agent, and were used in 1,2-insertion reactions.541.39QD ChemistryUniversity of Birminghamhttps://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.524882http://etheses.bham.ac.uk//id/eprint/1222/Electronic Thesis or Dissertation |
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541.39 QD Chemistry |
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541.39 QD Chemistry Martin, Nicolas Gold-catalysed reactions of Nitrogen containing molecules |
description |
The development of several new gold-catalysed reactions are described. Two new strategies have been employed to access pyrroles by the cycloisomerisation of alkynyl aziridines, and the formation of α,β-unsaturated imides by the oxidation of ynamides has been developed. A rare gold-mediated vinylidene rearrangement of brominated or silylated alkynes has been used to prepare brominated or silylated 2,4-substituted pyrroles regioselectively. The practical applicability of this process was limited by instability of products under the reaction conditions. Cationic gold catalysis was used in a synthesis of 2,4- and 2,5-substituted pyrroles from alkynyl aziridines. The role of counterion in these processes was studied and shown to be important in determining reaction outcomes. A Ph\(_3\)PAuCl/AgOTs catalyst system, allows 2,5-substituted pyrroles to be regioselectively synthesised in an atom-economical manner in near quantitative yield. From the same aryl-substituted starting materials the 2,4-substituted pyrrole isomer were accessed preferentially when a Ph\(_3\)PAuCl/AgOTf catalytic system was employed. A reaction mechanism accounting for the reaction outcome was proposed on the basis of \({^13}\)C- and deuterium-labelling studies. A new gold-catalysed synthesis of α,β-unsaturated imides was developed using a ynamide oxidation approach. Gold carbenoid intermediates can be formed regioselectively by action of an external oxidising agent, and were used in 1,2-insertion reactions. |
author |
Martin, Nicolas |
author_facet |
Martin, Nicolas |
author_sort |
Martin, Nicolas |
title |
Gold-catalysed reactions of Nitrogen containing molecules |
title_short |
Gold-catalysed reactions of Nitrogen containing molecules |
title_full |
Gold-catalysed reactions of Nitrogen containing molecules |
title_fullStr |
Gold-catalysed reactions of Nitrogen containing molecules |
title_full_unstemmed |
Gold-catalysed reactions of Nitrogen containing molecules |
title_sort |
gold-catalysed reactions of nitrogen containing molecules |
publisher |
University of Birmingham |
publishDate |
2010 |
url |
https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.524882 |
work_keys_str_mv |
AT martinnicolas goldcatalysedreactionsofnitrogencontainingmolecules |
_version_ |
1719013992426373120 |