{"id":{"repo_id":"cork","oai_identifier":"oai:cora.ucc.ie:10468/17000"},"canonical_url":"https://search.dev.ndltd.org/etd/cork/oai:cora.ucc.ie:10468/17000","repository":{"repo_id":"cork","name":"University College Cork","base_url":"https://cora.ucc.ie/server/oai/request"},"display":{"title":"Photochemical transformations of α-diazocarbonyl compounds in flow","abstract":"This thesis describes a detailed investigation of the synthetic and mechanistic aspects of the reactivity of a series of α-diazocarbonyl compounds including aryldiazoacetates, α-diazo-β-ketoesters and an α-diazo-β-ketosulfone, under continuous flow photolysis. These photochemical transformations yielded 2,3-dihydrobenzofurans, γ- and β-lactones, oxazoles and Wolff rearrangement products indicating the synthetic versatility of these metal-free processes. Continuous flow technology was also applied to telescope sulfonyl azide generation, diazo transfer and subsequent photochemical reactions, enabling three steps to be carried out without the need to isolate or handle any hazardous materials. The use of Process Analytical Technologies (FlowNMR and FlowIR™) throughout this work provided key insights into reaction progress and offered improved process safety through reaction monitoring.","abstract_html":"This thesis describes a detailed investigation of the synthetic and mechanistic aspects of the reactivity of a series of α-diazocarbonyl compounds including aryldiazoacetates, α-diazo-β-ketoesters and an α-diazo-β-ketosulfone, under continuous flow photolysis. These photochemical transformations yielded 2,3-dihydrobenzofurans, γ- and β-lactones, oxazoles and Wolff rearrangement products indicating the synthetic versatility of these metal-free processes. Continuous flow technology was also applied to telescope sulfonyl azide generation, diazo transfer and subsequent photochemical reactions, enabling three steps to be carried out without the need to isolate or handle any hazardous materials. The use of Process Analytical Technologies (FlowNMR and FlowIR™) throughout this work provided key insights into reaction progress and offered improved process safety through reaction monitoring.","abstract_has_math":false,"creators":["O'Callaghan, Katie S."],"institution":"University College Cork","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Maguire, Anita","Collins, Stuart"],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024","date_published":"2024","updated_at":"2026-07-24T01:47:07Z","subjects":["α-Diazocarbonyl compounds","Photochemistry","Flow chemistry"],"languages":["en"],"rights":["© 2024, Katie O'Callaghan."],"rights_urls":["https://creativecommons.org/licenses/by/4.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/10468/17000","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Maguire, Anita","Collins, Stuart"]},{"key":"dc:creator","label":"Author","values":["O'Callaghan, Katie S."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-02-06T15:03:19Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-02-06T15:03:19Z"]},{"key":"dc:date.issued","label":"Date","values":["2024"]},{"key":"dc:publisher","label":"Institution","values":["University College Cork"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD - Doctor of Philosophy"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["α-Diazocarbonyl compounds","Photochemistry","Flow chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["© 2024, Katie O'Callaghan."]},{"key":"dc:rights.uri","label":"Rights URI","values":["https://creativecommons.org/licenses/by/4.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10468/17000"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis describes a detailed investigation of the synthetic and mechanistic aspects of the reactivity of a series of α-diazocarbonyl compounds including aryldiazoacetates, α-diazo-β-ketoesters and an α-diazo-β-ketosulfone, under continuous flow photolysis. These photochemical transformations yielded 2,3-dihydrobenzofurans, γ- and β-lactones, oxazoles and Wolff rearrangement products indicating the synthetic versatility of these metal-free processes. Continuous flow technology was also applied to telescope sulfonyl azide generation, diazo transfer and subsequent photochemical reactions, enabling three steps to be carried out without the need to isolate or handle any hazardous materials. The use of Process Analytical Technologies (FlowNMR and FlowIR™) throughout this work provided key insights into reaction progress and offered improved process safety through reaction monitoring."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Photochemical transformations of α-diazocarbonyl compounds in flow"]}]}],"canonical_facts":{"dc:contributor.advisor":["Maguire, Anita","Collins, Stuart"],"dc:creator":["O'Callaghan, Katie S."],"dc:date.accessioned":["2025-02-06T15:03:19Z"],"dc:date.available":["2025-02-06T15:03:19Z"],"dc:date.issued":["2024"],"dc:description.abstract":["This thesis describes a detailed investigation of the synthetic and mechanistic aspects of the reactivity of a series of α-diazocarbonyl compounds including aryldiazoacetates, α-diazo-β-ketoesters and an α-diazo-β-ketosulfone, under continuous flow photolysis. These photochemical transformations yielded 2,3-dihydrobenzofurans, γ- and β-lactones, oxazoles and Wolff rearrangement products indicating the synthetic versatility of these metal-free processes. Continuous flow technology was also applied to telescope sulfonyl azide generation, diazo transfer and subsequent photochemical reactions, enabling three steps to be carried out without the need to isolate or handle any hazardous materials. The use of Process Analytical Technologies (FlowNMR and FlowIR™) throughout this work provided key insights into reaction progress and offered improved process safety through reaction monitoring."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://hdl.handle.net/10468/17000"],"dc:language.iso":["en"],"dc:publisher":["University College Cork"],"dc:rights":["© 2024, Katie O'Callaghan."],"dc:rights.uri":["https://creativecommons.org/licenses/by/4.0/"],"dc:subject":["α-Diazocarbonyl compounds","Photochemistry","Flow chemistry"],"dc:title":["Photochemical transformations of α-diazocarbonyl compounds in flow"],"dc:type":["Doctoral thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD - Doctor of Philosophy"]},"updated_at":"2026-07-24T01:47:07Z"}