{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/88216"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/88216","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of novel methodologies utilizing quaternary ammonium salts as catalysts","abstract":"The first half of this thesis (Chapter 2) described the development of a fluoride-promoted conjugate addition of sulfur-stabilized carbanion nucleophiles to α,β-unsaturated ketones and esters. This reaction was achieved using a substoichiometric amount of TBAF, resulting in high yields on the desired 1,4-addition product. The addition of 1,3-dithianes was given particular focus as a novel method for the preparation of differentially protect 1,4-dicarbonyl compounds. Observation by 13C NMR spectroscopy provided evidence that the reaction proceeds through an ion pair, and attempts to extend this reaction to asymmetric additions using a chiral counterion are presented in detail. The second half of this thesis (Chapter 3) details development of a phase transfer catalyzed [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds. Initial investigation focused on identifying viable substrate classes that would undergo selective [2,3]-rearrangement under phase transfer conditions. Under certain conditions, the [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds takes place in the presence of a phase transfer agent, providing a rare example of a phase transfer catalyzed unimolecular reaction. In the course of this investigation it was found that catalysis is dependent on several variables including base concentration, catalyst structure, and substrate lipophilicity. Preliminary testing of chiral, non-racemic phase transfer catalysts has shown promising levels of enantioselectivity for future development.","abstract_html":"The first half of this thesis (Chapter 2) described the development of a fluoride-promoted conjugate addition of sulfur-stabilized carbanion nucleophiles to α,β-unsaturated ketones and esters. This reaction was achieved using a substoichiometric amount of TBAF, resulting in high yields on the desired 1,4-addition product. The addition of 1,3-dithianes was given particular focus as a novel method for the preparation of differentially protect 1,4-dicarbonyl compounds. Observation by 13C NMR spectroscopy provided evidence that the reaction proceeds through an ion pair, and attempts to extend this reaction to asymmetric additions using a chiral counterion are presented in detail. The second half of this thesis (Chapter 3) details development of a phase transfer catalyzed [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds. Initial investigation focused on identifying viable substrate classes that would undergo selective [2,3]-rearrangement under phase transfer conditions. Under certain conditions, the [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds takes place in the presence of a phase transfer agent, providing a rare example of a phase transfer catalyzed unimolecular reaction. In the course of this investigation it was found that catalysis is dependent on several variables including base concentration, catalyst structure, and substrate lipophilicity. Preliminary testing of chiral, non-racemic phase transfer catalysts has shown promising levels of enantioselectivity for future development.","abstract_has_math":false,"creators":["Cullen, Lindsey R"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Denmark, Scott E.","Burke, Martin D.","Zimmerman, Steven C.","Silverman, Scott K."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-29T20:50:19Z","date_published":"2015-09-29T20:50:19Z","updated_at":"2026-07-22T22:26:31Z","subjects":["Phase Transfer Catalysis"],"languages":["en"],"rights":["Copyright Lindsey Cullen 2015"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/88216","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E.","Burke, Martin D.","Zimmerman, Steven C.","Silverman, Scott K."]},{"key":"dc:creator","label":"Author","values":["Cullen, Lindsey R"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-29T20:50:19Z","2017-09-30T09:15:38Z","2015-08","2015-07-17","2015-8"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Phase Transfer Catalysis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright Lindsey Cullen 2015"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/88216"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The first half of this thesis (Chapter 2) described the development of a fluoride-promoted conjugate addition of sulfur-stabilized carbanion nucleophiles to α,β-unsaturated ketones and esters. This reaction was achieved using a substoichiometric amount of TBAF, resulting in high yields on the desired 1,4-addition product. The addition of 1,3-dithianes was given particular focus as a novel method for the preparation of differentially protect 1,4-dicarbonyl compounds. Observation by 13C NMR spectroscopy provided evidence that the reaction proceeds through an ion pair, and attempts to extend this reaction to asymmetric additions using a chiral counterion are presented in detail. The second half of this thesis (Chapter 3) details development of a phase transfer catalyzed [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds. Initial investigation focused on identifying viable substrate classes that would undergo selective [2,3]-rearrangement under phase transfer conditions. Under certain conditions, the [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds takes place in the presence of a phase transfer agent, providing a rare example of a phase transfer catalyzed unimolecular reaction. In the course of this investigation it was found that catalysis is dependent on several variables including base concentration, catalyst structure, and substrate lipophilicity. Preliminary testing of chiral, non-racemic phase transfer catalysts has shown promising levels of enantioselectivity for future development.","Submission published under a 24 month embargo labeled 'U of I only', the embargo will last until 2017-08-01","The student, Lindsey Cullen, accepted the attached license on 2015-07-17 at 14:10.","The student, Lindsey Cullen, submitted this Dissertation for approval on 2015-07-17 at 14:17.","This Dissertation was approved for publication on 2015-07-17 at 16:21.","DSpace SAF Submission Ingestion Package generated from Vireo submission #8540 on 2015-09-29 at 15:00:48","Made available in DSpace on 2015-09-29T20:50:19Z (GMT). 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This reaction was achieved using a substoichiometric amount of TBAF, resulting in high yields on the desired 1,4-addition product. The addition of 1,3-dithianes was given particular focus as a novel method for the preparation of differentially protect 1,4-dicarbonyl compounds. Observation by 13C NMR spectroscopy provided evidence that the reaction proceeds through an ion pair, and attempts to extend this reaction to asymmetric additions using a chiral counterion are presented in detail. The second half of this thesis (Chapter 3) details development of a phase transfer catalyzed [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds. Initial investigation focused on identifying viable substrate classes that would undergo selective [2,3]-rearrangement under phase transfer conditions. Under certain conditions, the [2,3]-sigmatropic rearrangement of allyloxy carbonyl compounds takes place in the presence of a phase transfer agent, providing a rare example of a phase transfer catalyzed unimolecular reaction. In the course of this investigation it was found that catalysis is dependent on several variables including base concentration, catalyst structure, and substrate lipophilicity. Preliminary testing of chiral, non-racemic phase transfer catalysts has shown promising levels of enantioselectivity for future development.","Submission published under a 24 month embargo labeled 'U of I only', the embargo will last until 2017-08-01","The student, Lindsey Cullen, accepted the attached license on 2015-07-17 at 14:10.","The student, Lindsey Cullen, submitted this Dissertation for approval on 2015-07-17 at 14:17.","This Dissertation was approved for publication on 2015-07-17 at 16:21.","DSpace SAF Submission Ingestion Package generated from Vireo submission #8540 on 2015-09-29 at 15:00:48","Made available in DSpace on 2015-09-29T20:50:19Z (GMT). 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