{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/113823"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/113823","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of a Lewis base catalyzed, sulfenium-ion initiated enantioselective, spiroketalization cascade","abstract":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-04-06 without embargo terms","abstract_html":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-04-06 without embargo terms","abstract_has_math":false,"creators":["Hilby, Kimberly Muno"],"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","Hergenrother, Paul","Chan, Jefferson","Sarlah, David"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-04-29T21:34:12Z","date_published":"2022-04-29T21:34:12Z","updated_at":"2026-07-22T22:24:53Z","subjects":["Chemistry"],"languages":["en","eng"],"rights":["Copyright 2021 Kimberly Hilby"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/113823","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E","Hergenrother, Paul","Chan, Jefferson","Sarlah, David"]},{"key":"dc:creator","label":"Author","values":["Hilby, Kimberly Muno"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-04-29T21:34:12Z","2021-12","2021-10-26"]},{"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":["Chemistry"]}]},{"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 2021 Kimberly Hilby"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/113823"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-04-06 without embargo terms","The student, Kimberly Hilby, accepted the attached license on 2021-10-15 at 15:58.","The student, Kimberly Hilby, submitted this Dissertation for approval on 2021-10-15 at 16:11.","This Dissertation was approved for publication on 2021-10-26 at 09:14.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17164 on 2022-04-06 at 17:09:16","Made available in DSpace on 2022-04-29T21:34:12Z (GMT). No. of bitstreams: 3 HILBY-DISSERTATION-2021.pdf: 3151546 bytes, checksum: c5d7a84426bfa0645dd7a13df42a2780 (MD5) LICENSE.txt: 4211 bytes, checksum: 72f3d4237e6f887285cef784f8810a3d (MD5) PROQUEST_LICENSE.txt: 4557 bytes, checksum: e879fcdb35da1dd2894e2f7e65155587 (MD5) Previous issue date: 2021-10-26","This thesis covers the development of a Lewis base-catalyzed, enantioselective sulfenocyclization of olefins to afford [6,6]-spiroketals. Starting with an introduction on Lewis base catalysis and the prior work done in asymmetric spiroketalization cyclizations (Chapter 1), the thesis will then focus on the development of different synthetic routes towards the different substrate classes that were explored in the reaction: 1) alkyl-tethered alcohols, 2) phenol tethered alcohols and finally 3) benzyl-tethered alcohols (Chapter 2). Finally, the optimization and exploration of a sulfenion-ion initiated spiroketalization reaction (Chapter 3). The method uses a chiral Lewis base catalyst with an electrophilic sulfur source to generate enantioenriched thiiranium ion with alkenes. Upon formation, the thiiranium ion is subsequently captured in a cascade-type reaction, wherein a ketone oxygen serves as the nucleophile to open the thiiranium ion and an alcohol provides the secondary cyclization to form biorelevant spiroketals. A variety of electron-rich and electron-neutral E-substituted styrenes form the desired spiroketals in good yields with excellent enantio- and diastereoselectivities. Alkyl-substituted and terminal olefins participate in the cascade reaction, but with a limited scope compared to the styrenyl substrates. Benzofused substrates were found to be competent and provide a variety of different substituted benzofused spiroketals in good yields, enantioseletivities and diastereoselectivities. Finally, the future directions of this project are explored: 1) further mechanistic studies to elucidate the mechanism of the reactions using computational chemistry 2) the application to the total synthesis of benzofused [6,6]-spiroketals and 3) the application towards the synthesis of [5,5] and [5,6] spiroketals."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Development of a Lewis base catalyzed, sulfenium-ion initiated enantioselective, spiroketalization cascade"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E","Hergenrother, Paul","Chan, Jefferson","Sarlah, David"],"dc:creator":["Hilby, Kimberly Muno"],"dc:date":["2022-04-29T21:34:12Z","2021-12","2021-10-26"],"dc:description":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-04-06 without embargo terms","The student, Kimberly Hilby, accepted the attached license on 2021-10-15 at 15:58.","The student, Kimberly Hilby, submitted this Dissertation for approval on 2021-10-15 at 16:11.","This Dissertation was approved for publication on 2021-10-26 at 09:14.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17164 on 2022-04-06 at 17:09:16","Made available in DSpace on 2022-04-29T21:34:12Z (GMT). No. of bitstreams: 3 HILBY-DISSERTATION-2021.pdf: 3151546 bytes, checksum: c5d7a84426bfa0645dd7a13df42a2780 (MD5) LICENSE.txt: 4211 bytes, checksum: 72f3d4237e6f887285cef784f8810a3d (MD5) PROQUEST_LICENSE.txt: 4557 bytes, checksum: e879fcdb35da1dd2894e2f7e65155587 (MD5) Previous issue date: 2021-10-26","This thesis covers the development of a Lewis base-catalyzed, enantioselective sulfenocyclization of olefins to afford [6,6]-spiroketals. Starting with an introduction on Lewis base catalysis and the prior work done in asymmetric spiroketalization cyclizations (Chapter 1), the thesis will then focus on the development of different synthetic routes towards the different substrate classes that were explored in the reaction: 1) alkyl-tethered alcohols, 2) phenol tethered alcohols and finally 3) benzyl-tethered alcohols (Chapter 2). Finally, the optimization and exploration of a sulfenion-ion initiated spiroketalization reaction (Chapter 3). The method uses a chiral Lewis base catalyst with an electrophilic sulfur source to generate enantioenriched thiiranium ion with alkenes. Upon formation, the thiiranium ion is subsequently captured in a cascade-type reaction, wherein a ketone oxygen serves as the nucleophile to open the thiiranium ion and an alcohol provides the secondary cyclization to form biorelevant spiroketals. A variety of electron-rich and electron-neutral E-substituted styrenes form the desired spiroketals in good yields with excellent enantio- and diastereoselectivities. Alkyl-substituted and terminal olefins participate in the cascade reaction, but with a limited scope compared to the styrenyl substrates. Benzofused substrates were found to be competent and provide a variety of different substituted benzofused spiroketals in good yields, enantioseletivities and diastereoselectivities. Finally, the future directions of this project are explored: 1) further mechanistic studies to elucidate the mechanism of the reactions using computational chemistry 2) the application to the total synthesis of benzofused [6,6]-spiroketals and 3) the application towards the synthesis of [5,5] and [5,6] spiroketals."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/113823"],"dc:language":["en","eng"],"dc:rights":["Copyright 2021 Kimberly Hilby"],"dc:subject":["Chemistry"],"dc:title":["Development of a Lewis base catalyzed, sulfenium-ion initiated enantioselective, spiroketalization cascade"],"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":"2026-07-22T22:24:53Z"}