{"id":{"repo_id":"ottawa-retro","oai_identifier":"oai:ruor.uottawa.ca:10393/29432"},"canonical_url":"https://search.dev.ndltd.org/etd/ottawa-retro/oai:ruor.uottawa.ca:10393/29432","repository":{"repo_id":"ottawa-retro","name":"University of Ottawa","base_url":"https://ruor.uottawa.ca/server/oai/request"},"display":{"title":"Part A The application of fluorescence resonance energy transfer to reaction discovery Part B The stereodefined synthesis of tetrasubstituted olefins","abstract":"In part A, the development of methodology for enantioselective reaction monitoring using Fluorescence Resonance Energy Transfer (FRET) is described. The syntheses of enantiomeric epoxides bearing different fluorescent donors and a phenol that bore fluorescence acceptor were explored.* Part B describes the stereodefined synthesis of tetrasubstituted olefins. 2-Alkynyl esters were selectively converted to E-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. These products were produced cleanly, regio- and stereoselectively, and in high yields. The treatment of the same substrates with ICI produced mixtures of isomers. Mechanistic studies indicated that ICI was the most plausible intermediate and that a Bu4NI-ICI complex was likely responsible for the high selectivity observed in the Bu4NI/DCE system.* The Bu4NI/DCE system was shown to be selective for the chlorination of alkenes. The treatment of the same alkenes with ICI returned a mixture of chlorinated and iodochlorinated products. In addition, the Bu4NI/DCE system was chemoselective in substrates bearing both aromatic and olefinic moieties, reacting at the alkenyl functionality exclusively. Exposure of these substrates to ICI produced a mixture of products.* The halogenated olefins produced in the initial study were employed as olefin templates for the formation of tetrasubstituted olefins. Regioselective and stereospecific palladium-catalyzed cross-coupling reactions were employed to incorporate a wide variety of substituents into the highly congested olefins, affording single isomer products in good yields.* *Please refer to dissertation for diagrams.","abstract_html":"In part A, the development of methodology for enantioselective reaction monitoring using Fluorescence Resonance Energy Transfer (FRET) is described. The syntheses of enantiomeric epoxides bearing different fluorescent donors and a phenol that bore fluorescence acceptor were explored.* Part B describes the stereodefined synthesis of tetrasubstituted olefins. 2-Alkynyl esters were selectively converted to E-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. These products were produced cleanly, regio- and stereoselectively, and in high yields. The treatment of the same substrates with ICI produced mixtures of isomers. Mechanistic studies indicated that ICI was the most plausible intermediate and that a Bu4NI-ICI complex was likely responsible for the high selectivity observed in the Bu4NI/DCE system.* The Bu4NI/DCE system was shown to be selective for the chlorination of alkenes. The treatment of the same alkenes with ICI returned a mixture of chlorinated and iodochlorinated products. In addition, the Bu4NI/DCE system was chemoselective in substrates bearing both aromatic and olefinic moieties, reacting at the alkenyl functionality exclusively. Exposure of these substrates to ICI produced a mixture of products.* The halogenated olefins produced in the initial study were employed as olefin templates for the formation of tetrasubstituted olefins. Regioselective and stereospecific palladium-catalyzed cross-coupling reactions were employed to incorporate a wide variety of substituents into the highly congested olefins, affording single isomer products in good yields.* *Please refer to dissertation for diagrams.","abstract_has_math":false,"creators":["Flynn, Alison B"],"institution":"University of Ottawa (Canada)","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-11-08T16:07:23Z","date_published":"2013-11-08T16:07:23Z","updated_at":"2026-07-24T03:39:38Z","subjects":["Chemistry, Organic."],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Dissertation Abstracts International, Volume: 68-10, Section: B, page: 6665.","http://dx.doi.org/10.20381/ruor-19745"],"render_values":[{"text":"Source: Dissertation Abstracts International, Volume: 68-10, Section: B, page: 6665.","href":null,"code":true},{"text":"http://dx.doi.org/10.20381/ruor-19745","href":"http://dx.doi.org/10.20381/ruor-19745","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10393/29432","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Flynn, Alison B"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013-11-08T16:07:23Z","2007"]},{"key":"dc:publisher","label":"Institution","values":["University of Ottawa (Canada)"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Dissertation Abstracts International, Volume: 68-10, Section: B, page: 6665.","http://hdl.handle.net/10393/29432","http://dx.doi.org/10.20381/ruor-19745"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In part A, the development of methodology for enantioselective reaction monitoring using Fluorescence Resonance Energy Transfer (FRET) is described. The syntheses of enantiomeric epoxides bearing different fluorescent donors and a phenol that bore fluorescence acceptor were explored.* Part B describes the stereodefined synthesis of tetrasubstituted olefins. 2-Alkynyl esters were selectively converted to E-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. These products were produced cleanly, regio- and stereoselectively, and in high yields. The treatment of the same substrates with ICI produced mixtures of isomers. Mechanistic studies indicated that ICI was the most plausible intermediate and that a Bu4NI-ICI complex was likely responsible for the high selectivity observed in the Bu4NI/DCE system.* The Bu4NI/DCE system was shown to be selective for the chlorination of alkenes. The treatment of the same alkenes with ICI returned a mixture of chlorinated and iodochlorinated products. In addition, the Bu4NI/DCE system was chemoselective in substrates bearing both aromatic and olefinic moieties, reacting at the alkenyl functionality exclusively. Exposure of these substrates to ICI produced a mixture of products.* The halogenated olefins produced in the initial study were employed as olefin templates for the formation of tetrasubstituted olefins. Regioselective and stereospecific palladium-catalyzed cross-coupling reactions were employed to incorporate a wide variety of substituents into the highly congested olefins, affording single isomer products in good yields.* *Please refer to dissertation for diagrams."]},{"key":"dc:format","label":"Dc Format","values":["392 p.","application/pdf"]},{"key":"dc:title","label":"Title","values":["Part A The application of fluorescence resonance energy transfer to reaction discovery Part B The stereodefined synthesis of tetrasubstituted olefins"]}]}],"canonical_facts":{"dc:creator":["Flynn, Alison B"],"dc:date":["2013-11-08T16:07:23Z","2007"],"dc:description":["In part A, the development of methodology for enantioselective reaction monitoring using Fluorescence Resonance Energy Transfer (FRET) is described. The syntheses of enantiomeric epoxides bearing different fluorescent donors and a phenol that bore fluorescence acceptor were explored.* Part B describes the stereodefined synthesis of tetrasubstituted olefins. 2-Alkynyl esters were selectively converted to E-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. These products were produced cleanly, regio- and stereoselectively, and in high yields. The treatment of the same substrates with ICI produced mixtures of isomers. Mechanistic studies indicated that ICI was the most plausible intermediate and that a Bu4NI-ICI complex was likely responsible for the high selectivity observed in the Bu4NI/DCE system.* The Bu4NI/DCE system was shown to be selective for the chlorination of alkenes. The treatment of the same alkenes with ICI returned a mixture of chlorinated and iodochlorinated products. In addition, the Bu4NI/DCE system was chemoselective in substrates bearing both aromatic and olefinic moieties, reacting at the alkenyl functionality exclusively. Exposure of these substrates to ICI produced a mixture of products.* The halogenated olefins produced in the initial study were employed as olefin templates for the formation of tetrasubstituted olefins. Regioselective and stereospecific palladium-catalyzed cross-coupling reactions were employed to incorporate a wide variety of substituents into the highly congested olefins, affording single isomer products in good yields.* *Please refer to dissertation for diagrams."],"dc:format":["392 p.","application/pdf"],"dc:identifier":["Source: Dissertation Abstracts International, Volume: 68-10, Section: B, page: 6665.","http://hdl.handle.net/10393/29432","http://dx.doi.org/10.20381/ruor-19745"],"dc:language":["en"],"dc:publisher":["University of Ottawa (Canada)"],"dc:subject":["Chemistry, Organic."],"dc:title":["Part A The application of fluorescence resonance energy transfer to reaction discovery Part B The stereodefined synthesis of tetrasubstituted olefins"],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:39:38Z"}