{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/120368"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/120368","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Enantioselective alkene difunctionalization enabled by organochalcogen catalysis I. Lewis base-catalyzed sulfenium ion transfer II. Organoselenium redox catalysis","abstract":"Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2025-05-01","abstract_html":"Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2025-05-01","abstract_has_math":false,"creators":["Panger, Jesse Lee"],"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","Sarlah, David","Girolami, Gregory S","Mirica, Liviu M"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023-05","date_published":"2023-05","updated_at":"2026-07-22T22:24:57Z","subjects":["Organocatalysis","Chalcogen","Enantioselective","Sulfenofunctionalization","Lewis Base Catalysis"],"languages":["en","eng"],"rights":["Copyright 2023, Jesse Panger"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/120368","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E","Sarlah, David","Girolami, Gregory S","Mirica, Liviu M"]},{"key":"dc:creator","label":"Author","values":["Panger, Jesse Lee"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2023-05","2023-04-25"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"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":["Organocatalysis","Chalcogen","Enantioselective","Sulfenofunctionalization","Lewis Base Catalysis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2023, Jesse Panger"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/120368"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2025-05-01","The student, Jesse Panger, accepted the attached license on 2023-04-13 at 13:58.","The student, Jesse Panger, submitted this Dissertation for approval on 2023-04-13 at 14:21.","This Dissertation was approved for publication on 2023-04-25 at 15:53.","DSpace SAF Submission Ingestion Package generated from Vireo submission #18979 on 2023-09-01 at 17:13:27","The thesis herein will cover broadly the application of main group organoselenium catalysis for: (1) the enantioselective transfer of sulfenium ions to alkenes to form lactams, (2) the enantioselective transfer of sulfenium ions to specifically Z-alkenes and the physical organic differences in reactivity between E- and Z-alkenes, and (3) diselenide-catalyzed syn-difunctionalization of alkenes under an oxidative manifold. A further appendix will include work toward the activation and utilization of nitrenium ions for enantioselective aziridination which ultimately was not successful but has important foundational work conducted. Chapter 1 will cover the background of Lewis base catalysis and its application in organic synthesis. Then it will transition into enantioselective sulfenium ion transfer and how the Denmark laboratory has found success with different nucleophiles to afford attractive sulfenofunctionalized products (Chapter 2). These products can be rapidly diversified into a wide variety of useful products under operationally simple transformations. Chapter 3 will expand on the previous discussion by showcasing examples where earlier methodology overlooked critical insights into the catalyst/alkene combination. These studies include both a physical organic look at the mechanism as well as the synthetic applicability. Chapter 4 will change focus to organoselenium redox catalysis whereby a highly electrophilic selenium species becomes susceptible to displacement by careful choice of nucleophile. The selenium species undergoes two displacements to render the whole process catalytic in selenium, a stark contrast to the sulfenofunctionalization discussed in chapters 1-3. The key finding of the addition of fluoride scavengers has the effect of enhancing reactivity in some cases, and in other cases fully ‘turning on’ reactivity. Using a fluoride scavenger has opened up the platform for what is possible under the reaction manifold utilized in these laboratories."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Enantioselective alkene difunctionalization enabled by organochalcogen catalysis I. Lewis base-catalyzed sulfenium ion transfer II. Organoselenium redox catalysis"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E","Sarlah, David","Girolami, Gregory S","Mirica, Liviu M"],"dc:creator":["Panger, Jesse Lee"],"dc:date":["2023-05","2023-04-25"],"dc:description":["Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2025-05-01","The student, Jesse Panger, accepted the attached license on 2023-04-13 at 13:58.","The student, Jesse Panger, submitted this Dissertation for approval on 2023-04-13 at 14:21.","This Dissertation was approved for publication on 2023-04-25 at 15:53.","DSpace SAF Submission Ingestion Package generated from Vireo submission #18979 on 2023-09-01 at 17:13:27","The thesis herein will cover broadly the application of main group organoselenium catalysis for: (1) the enantioselective transfer of sulfenium ions to alkenes to form lactams, (2) the enantioselective transfer of sulfenium ions to specifically Z-alkenes and the physical organic differences in reactivity between E- and Z-alkenes, and (3) diselenide-catalyzed syn-difunctionalization of alkenes under an oxidative manifold. A further appendix will include work toward the activation and utilization of nitrenium ions for enantioselective aziridination which ultimately was not successful but has important foundational work conducted. Chapter 1 will cover the background of Lewis base catalysis and its application in organic synthesis. Then it will transition into enantioselective sulfenium ion transfer and how the Denmark laboratory has found success with different nucleophiles to afford attractive sulfenofunctionalized products (Chapter 2). These products can be rapidly diversified into a wide variety of useful products under operationally simple transformations. Chapter 3 will expand on the previous discussion by showcasing examples where earlier methodology overlooked critical insights into the catalyst/alkene combination. These studies include both a physical organic look at the mechanism as well as the synthetic applicability. Chapter 4 will change focus to organoselenium redox catalysis whereby a highly electrophilic selenium species becomes susceptible to displacement by careful choice of nucleophile. The selenium species undergoes two displacements to render the whole process catalytic in selenium, a stark contrast to the sulfenofunctionalization discussed in chapters 1-3. The key finding of the addition of fluoride scavengers has the effect of enhancing reactivity in some cases, and in other cases fully ‘turning on’ reactivity. Using a fluoride scavenger has opened up the platform for what is possible under the reaction manifold utilized in these laboratories."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/120368"],"dc:language":["en","eng"],"dc:rights":["Copyright 2023, Jesse Panger"],"dc:subject":["Organocatalysis","Chalcogen","Enantioselective","Sulfenofunctionalization","Lewis Base Catalysis"],"dc:title":["Enantioselective alkene difunctionalization enabled by organochalcogen catalysis I. Lewis base-catalyzed sulfenium ion transfer II. Organoselenium redox catalysis"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:57Z"}