{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/115652"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/115652","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The development of dearomative functionalizations and their use in the total synthesis of bioactive natural products","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2024-05-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2024-05-01","abstract_has_math":false,"creators":["Bingham, Tanner William"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Sarlah, David","Denmark, Scott E","Hergenrother, Paul J","White, Christina M"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-05","date_published":"2022-05","updated_at":"2026-07-22T22:24:54Z","subjects":["Total Synthesis","Scalability","Dearomatization","Aromatic Compounds","MTAD","Amaryllidaceae Isocarbostyril Alkaloids"],"languages":["en","eng"],"rights":["Copyright 2022 Tanner Bingham"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/115652","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Sarlah, David","Denmark, Scott E","Hergenrother, Paul J","White, Christina M"]},{"key":"dc:creator","label":"Author","values":["Bingham, Tanner William"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-05","2022-01-27"]},{"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":["Total Synthesis","Scalability","Dearomatization","Aromatic Compounds","MTAD","Amaryllidaceae Isocarbostyril Alkaloids"]}]},{"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 2022 Tanner Bingham"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/115652"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2024-05-01","The student, Tanner Bingham, accepted the attached license on 2022-01-21 at 12:43.","The student, Tanner Bingham, submitted this Dissertation for approval on 2022-01-21 at 13:02.","This Dissertation was approved for publication on 2022-01-27 at 15:35.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17482 on 2022-11-11 at 12:18:07","The dearomatization of aromatic compounds, some of the most abundant feedstock chemicals, has been heavily studied over the past century. Despite their widespread use, most methods for dearomatization do not result in the introduction of additional functionality. This dissertation describes the use of N-methyl-1,2,4-triazoline-3,5-dione (MTAD) in the development of various dearomative functionalization reactions as well as its use in the total synthesis of bioactive natural products. A total synthesis of the highly potent anticancer natural products, the Amaryllidaceae isocarbostyril alkaloids, was developed. The brevity and scalability of our synthesis was due to the development of a nickel-catalyzed asymmetric dearomative carboamination reaction, providing a stereodefined diene that provided facile access to the cyclitol core of these natural products. The utility of this dearomative functionalization reaction led us to explore similar types of reactivity, ultimately leading to the development of dearomative cyclopropanation, a dearomative Pauson-Khand reaction, and three different dearomative allylic substitution reactions — 1,4-hydroamination, trans-1,4- carboamination, and syn-1,2-diamination. We also explored the dearomative functionalization of heteroarenes and found that substituted pyridines were viable substrates. Dearomative dihydroxylation, diimide reduction, and epoxidation were all able to provide dearomatized products in synthetically useful yields. Further elaboration of these substrates was able to provide rapid access to substituted piperidines and piperidones."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The development of dearomative functionalizations and their use in the total synthesis of bioactive natural products"]}]}],"canonical_facts":{"dc:contributor":["Sarlah, David","Denmark, Scott E","Hergenrother, Paul J","White, Christina M"],"dc:creator":["Bingham, Tanner William"],"dc:date":["2022-05","2022-01-27"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2024-05-01","The student, Tanner Bingham, accepted the attached license on 2022-01-21 at 12:43.","The student, Tanner Bingham, submitted this Dissertation for approval on 2022-01-21 at 13:02.","This Dissertation was approved for publication on 2022-01-27 at 15:35.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17482 on 2022-11-11 at 12:18:07","The dearomatization of aromatic compounds, some of the most abundant feedstock chemicals, has been heavily studied over the past century. Despite their widespread use, most methods for dearomatization do not result in the introduction of additional functionality. This dissertation describes the use of N-methyl-1,2,4-triazoline-3,5-dione (MTAD) in the development of various dearomative functionalization reactions as well as its use in the total synthesis of bioactive natural products. A total synthesis of the highly potent anticancer natural products, the Amaryllidaceae isocarbostyril alkaloids, was developed. The brevity and scalability of our synthesis was due to the development of a nickel-catalyzed asymmetric dearomative carboamination reaction, providing a stereodefined diene that provided facile access to the cyclitol core of these natural products. The utility of this dearomative functionalization reaction led us to explore similar types of reactivity, ultimately leading to the development of dearomative cyclopropanation, a dearomative Pauson-Khand reaction, and three different dearomative allylic substitution reactions — 1,4-hydroamination, trans-1,4- carboamination, and syn-1,2-diamination. We also explored the dearomative functionalization of heteroarenes and found that substituted pyridines were viable substrates. Dearomative dihydroxylation, diimide reduction, and epoxidation were all able to provide dearomatized products in synthetically useful yields. Further elaboration of these substrates was able to provide rapid access to substituted piperidines and piperidones."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/115652"],"dc:language":["en","eng"],"dc:rights":["Copyright 2022 Tanner Bingham"],"dc:subject":["Total Synthesis","Scalability","Dearomatization","Aromatic Compounds","MTAD","Amaryllidaceae Isocarbostyril Alkaloids"],"dc:title":["The development of dearomative functionalizations and their use in the total synthesis of bioactive natural products"],"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":"2026-07-22T22:24:54Z"}