{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84148"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84148","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Tandem Cycloaddition Chemistry of Nitroalkenes: Total Synthesis of (+)-1-Epiaustraline and Synthesis of the Pentacyclic Core of (+/-)-Scandine","abstract":"The successful synthesis of the (+)-scandine core began with a tandem conjugate addition/ [3+2] nitronate cycloaddition. This approach proceeded with high chemical yield and modest diastereoselectivity to provide an advanced bicyclic intermediate. Construction of two of the remaining three rings was accomplished by an intramolecular Heck cyclization of a pendant aryl iodide. This process proceeded with high diastereoselectivity to build vicinal quaternary centers. The final ring was created by reductive amination of a pyrrolidine aldehyde. This synthesis provided the core structure of (+/-)-scandine in 16 steps and 4.8% overall yield from 2,4-pentadienyl dimethyl malonate.","abstract_html":"The successful synthesis of the (+)-scandine core began with a tandem conjugate addition/ [3+2] nitronate cycloaddition. This approach proceeded with high chemical yield and modest diastereoselectivity to provide an advanced bicyclic intermediate. Construction of two of the remaining three rings was accomplished by an intramolecular Heck cyclization of a pendant aryl iodide. This process proceeded with high diastereoselectivity to build vicinal quaternary centers. The final ring was created by reductive amination of a pyrrolidine aldehyde. This synthesis provided the core structure of (+/-)-scandine in 16 steps and 4.8% overall yield from 2,4-pentadienyl dimethyl malonate.","abstract_has_math":false,"creators":["Cottell, Jeromy John"],"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."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:13:11Z","date_published":"2015-09-25T22:13:11Z","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3153278"],"render_values":[{"text":"(MiAaPQ)AAI3153278","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84148","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E."]},{"key":"dc:creator","label":"Author","values":["Cottell, Jeromy John"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:13:11Z","10000-01-01","2004"]},{"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/2142/84148","(MiAaPQ)AAI3153278"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The successful synthesis of the (+)-scandine core began with a tandem conjugate addition/ [3+2] nitronate cycloaddition. This approach proceeded with high chemical yield and modest diastereoselectivity to provide an advanced bicyclic intermediate. Construction of two of the remaining three rings was accomplished by an intramolecular Heck cyclization of a pendant aryl iodide. This process proceeded with high diastereoselectivity to build vicinal quaternary centers. The final ring was created by reductive amination of a pyrrolidine aldehyde. This synthesis provided the core structure of (+/-)-scandine in 16 steps and 4.8% overall yield from 2,4-pentadienyl dimethyl malonate.","Made available in DSpace on 2015-09-25T22:13:11Z (GMT). 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This approach proceeded with high chemical yield and modest diastereoselectivity to provide an advanced bicyclic intermediate. Construction of two of the remaining three rings was accomplished by an intramolecular Heck cyclization of a pendant aryl iodide. This process proceeded with high diastereoselectivity to build vicinal quaternary centers. The final ring was created by reductive amination of a pyrrolidine aldehyde. This synthesis provided the core structure of (+/-)-scandine in 16 steps and 4.8% overall yield from 2,4-pentadienyl dimethyl malonate.","Made available in DSpace on 2015-09-25T22:13:11Z (GMT). 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