{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84409"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84409","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Tandem Inter [4+2]/[3+2] Cycloadditions of Nitroalkenes: The Bridged-Mode","abstract":"In continuing investigations, an asymmetric variant of the tandem inter $\\lbrack 4 + 2\\rbrack$/intra $\\lbrack 3 + 2\\rbrack$ bridged mode ($\\beta$-tether) cycloaddition of nitroalkenes has been developed. This new sequence involves the Lewis-acid-promoted $\\lbrack 4 + 2\\rbrack$ cycloaddition of a variety of nitro olefins with 1-alkoxy-1,4-pentadienes derived from (1R,2S)-phenylcyclohexanol. Intramolecular $\\lbrack 3 + 2\\rbrack$ cycloadditions afforded stable nitroso acetals that were reduced using nickel boride to provide enantiomerically enriched aminocyclopentanes in good yields and high enantiomeric excess. Additionally, the Lewis acid employed in the $\\lbrack 4 + 2\\rbrack$ cycloaddition was found to impart a remarkable influence on the stereochemical outcome of the tandem sequence.","abstract_html":"In continuing investigations, an asymmetric variant of the tandem inter $\\lbrack 4 + 2\\rbrack$/intra $\\lbrack 3 + 2\\rbrack$ bridged mode (<span class=\"etd-inline-math\">&beta;</span>-tether) cycloaddition of nitroalkenes has been developed. This new sequence involves the Lewis-acid-promoted $\\lbrack 4 + 2\\rbrack$ cycloaddition of a variety of nitro olefins with 1-alkoxy-1,4-pentadienes derived from (1R,2S)-phenylcyclohexanol. Intramolecular $\\lbrack 3 + 2\\rbrack$ cycloadditions afforded stable nitroso acetals that were reduced using nickel boride to provide enantiomerically enriched aminocyclopentanes in good yields and high enantiomeric excess. Additionally, the Lewis acid employed in the $\\lbrack 4 + 2\\rbrack$ cycloaddition was found to impart a remarkable influence on the stereochemical outcome of the tandem sequence.","abstract_has_math":true,"creators":["Dixon, Julie Ann"],"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":"2015-09-25T22:14:20Z","date_published":"2015-09-25T22:14:20Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9904433"],"render_values":[{"text":"(MiAaPQ)AAI9904433","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84409","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":["Dixon, Julie Ann"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:20Z","10000-01-01","1998"]},{"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/2142/84409","(MiAaPQ)AAI9904433"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In continuing investigations, an asymmetric variant of the tandem inter $\\lbrack 4 + 2\\rbrack$/intra $\\lbrack 3 + 2\\rbrack$ bridged mode ($\\beta$-tether) cycloaddition of nitroalkenes has been developed. This new sequence involves the Lewis-acid-promoted $\\lbrack 4 + 2\\rbrack$ cycloaddition of a variety of nitro olefins with 1-alkoxy-1,4-pentadienes derived from (1R,2S)-phenylcyclohexanol. Intramolecular $\\lbrack 3 + 2\\rbrack$ cycloadditions afforded stable nitroso acetals that were reduced using nickel boride to provide enantiomerically enriched aminocyclopentanes in good yields and high enantiomeric excess. Additionally, the Lewis acid employed in the $\\lbrack 4 + 2\\rbrack$ cycloaddition was found to impart a remarkable influence on the stereochemical outcome of the tandem sequence.","Made available in DSpace on 2015-09-25T22:14:20Z (GMT). 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This new sequence involves the Lewis-acid-promoted $\\lbrack 4 + 2\\rbrack$ cycloaddition of a variety of nitro olefins with 1-alkoxy-1,4-pentadienes derived from (1R,2S)-phenylcyclohexanol. Intramolecular $\\lbrack 3 + 2\\rbrack$ cycloadditions afforded stable nitroso acetals that were reduced using nickel boride to provide enantiomerically enriched aminocyclopentanes in good yields and high enantiomeric excess. Additionally, the Lewis acid employed in the $\\lbrack 4 + 2\\rbrack$ cycloaddition was found to impart a remarkable influence on the stereochemical outcome of the tandem sequence.","Made available in DSpace on 2015-09-25T22:14:20Z (GMT). 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