{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84279"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84279","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Asymmetric Total Synthesis of (+)-Nominine: Development of a Dual Cycloaddition Strategy for the Synthesis of the Hetisine Alkaloids","abstract":"A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed and applied to the asymmetric total synthesis of nominine. The approach relies on an early stage intramolecular aza-1,3-dipolar cycloaddition of a 4-oxidoisoquinolinium betaine with an ene-nitrile dipolarophile and a late stage intramolecular [4+2] Diels-Alder cycloaddition. Also of note is the development of a new method for the preparation of 4-oxidoisoquinolinium betaines. Overall, a 16 step asymmetric synthesis of (+)-nominine was accomplished in 1.3% yield, while (+/-)-nominine was prepared in 15 steps in 6.1% yield.","abstract_html":"A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed and applied to the asymmetric total synthesis of nominine. The approach relies on an early stage intramolecular aza-1,3-dipolar cycloaddition of a 4-oxidoisoquinolinium betaine with an ene-nitrile dipolarophile and a late stage intramolecular [4+2] Diels-Alder cycloaddition. Also of note is the development of a new method for the preparation of 4-oxidoisoquinolinium betaines. Overall, a 16 step asymmetric synthesis of (+)-nominine was accomplished in 1.3% yield, while (+/-)-nominine was prepared in 15 steps in 6.1% yield.","abstract_has_math":false,"creators":["Peese, Kevin M."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Gin, David Y."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":null,"date_issued":"10000-01-01","date_published":"10000-01-01","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3290348"],"render_values":[{"text":"(MiAaPQ)AAI3290348","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84279","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gin, David Y."]},{"key":"dc:creator","label":"Author","values":["Peese, Kevin M."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["10000-01-01","2007","2015-09-25T22:13:46Z"]},{"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":["Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84279","(MiAaPQ)AAI3290348"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed and applied to the asymmetric total synthesis of nominine. The approach relies on an early stage intramolecular aza-1,3-dipolar cycloaddition of a 4-oxidoisoquinolinium betaine with an ene-nitrile dipolarophile and a late stage intramolecular [4+2] Diels-Alder cycloaddition. Also of note is the development of a new method for the preparation of 4-oxidoisoquinolinium betaines. Overall, a 16 step asymmetric synthesis of (+)-nominine was accomplished in 1.3% yield, while (+/-)-nominine was prepared in 15 steps in 6.1% yield.","Made available in DSpace on 2015-09-25T22:13:46Z (GMT). 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The approach relies on an early stage intramolecular aza-1,3-dipolar cycloaddition of a 4-oxidoisoquinolinium betaine with an ene-nitrile dipolarophile and a late stage intramolecular [4+2] Diels-Alder cycloaddition. Also of note is the development of a new method for the preparation of 4-oxidoisoquinolinium betaines. Overall, a 16 step asymmetric synthesis of (+)-nominine was accomplished in 1.3% yield, while (+/-)-nominine was prepared in 15 steps in 6.1% yield.","Made available in DSpace on 2015-09-25T22:13:46Z (GMT). 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