{"id":{"repo_id":"birmingham","oai_identifier":"oai:etheses.bham.ac.uk:1222"},"canonical_url":"https://search.dev.ndltd.org/etd/birmingham/oai:etheses.bham.ac.uk:1222","repository":{"repo_id":"birmingham","name":"University of Birmingham","base_url":"https://etheses.bham.ac.uk/cgi/oai2"},"display":{"title":"Gold-catalysed reactions of Nitrogen containing molecules","abstract":"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.","abstract_html":"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<span class=\"etd-inline-math\"><sub>3</sub></span>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<span class=\"etd-inline-math\"><sub>3</sub></span>PAuCl/AgOTf catalytic system was employed. A reaction mechanism accounting for the reaction outcome was proposed on the basis of <span class=\"etd-inline-math\">{<sup>1</sup>3}</span>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.","abstract_has_math":true,"creators":["Martin, Nicolas"],"institution":"University of Birmingham","degree_name":"d_ph","degree_level":"d_ph","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010-12","date_published":"2010-12","updated_at":"2026-07-24T01:11:26Z","subjects":["QD Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.sponsor","label":"Sponsor","values":["epsrc"]},{"key":"dc:creator","label":"Author","values":["Martin, Nicolas"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010-12"]},{"key":"dc:date.issued","label":"Date","values":["2010-12"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["College of Engineering & Physical Sciences","School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Birmingham"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["http://etheses.bham.ac.uk//id/eprint/1222/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["d_ph"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["d_ph"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["QD Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://etheses.bham.ac.uk//id/eprint/1222/2/Decl_IS_Martin10PhD.pdf","http://etheses.bham.ac.uk//id/eprint/1222/3/Martin10PhD.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Gold-catalysed reactions of Nitrogen containing molecules"]}]}],"canonical_facts":{"dc:contributor.sponsor":["epsrc"],"dc:creator":["Martin, Nicolas"],"dc:date":["2010-12"],"dc:date.issued":["2010-12"],"dc:description.abstract":["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."],"dc:format":["application/pdf"],"dc:identifier.uri":["http://etheses.bham.ac.uk//id/eprint/1222/2/Decl_IS_Martin10PhD.pdf","http://etheses.bham.ac.uk//id/eprint/1222/3/Martin10PhD.pdf"],"dc:publisher.department":["College of Engineering & Physical Sciences","School of Chemistry"],"dc:publisher.institution":["University of Birmingham"],"dc:relation.isreferencedby":["http://etheses.bham.ac.uk//id/eprint/1222/"],"dc:subject":["QD Chemistry"],"dc:title":["Gold-catalysed reactions of Nitrogen containing molecules"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["d_ph"],"dc:type.qualificationname":["d_ph"]},"updated_at":"2026-07-24T01:11:26Z"}