{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72294"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72294","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Stereoselective Synthesis of Trisubstituted Olefins","abstract":"A new method for the highly stereoselective synthesis of trisubstituted olefins is presented. The method involves the stereoselective construction of various $\\beta$-hydroxy phosphonamidates followed by their thermolysis to provide trisubstituted olefins in extremely high geometrical purity ($&gt;$99/1).","abstract_html":"A new method for the highly stereoselective synthesis of trisubstituted olefins is presented. The method involves the stereoselective construction of various <span class=\"etd-inline-math\">&beta;</span>-hydroxy phosphonamidates followed by their thermolysis to provide trisubstituted olefins in extremely high geometrical purity ($&amp;gt;$99/1).","abstract_has_math":true,"creators":["Amburgey, Jack S."],"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":2014,"date_issued":"2014-12-17T21:29:13Z","date_published":"2014-12-17T21:29:13Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI9503130"],"render_values":[{"text":"(UMI)AAI9503130","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72294","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":["Amburgey, Jack S."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:29:13Z","10000-01-01","1994"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/72294","(UMI)AAI9503130"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A new method for the highly stereoselective synthesis of trisubstituted olefins is presented. The method involves the stereoselective construction of various $\\beta$-hydroxy phosphonamidates followed by their thermolysis to provide trisubstituted olefins in extremely high geometrical purity ($&gt;$99/1).","The stereoselective construction of $\\beta$-hydroxy phosphonamidates could be accomplished through three main synthetic transformations. The first involves the acylation of various parent 1,3,2-oxazaphospholidines to provide monoalkylated $\\beta$-keto phosphonamidates in good yield. The second step is the alkylation of the $\\beta$-keto phosphonamidates to provide $\\alpha,\\alpha$-dialkylated $\\beta$-keto phosphonamidates in high yield and very high diastereoselectivities. Finally, the highly diastereoselective reduction of the dialkylated $\\beta$-keto phosphonamidates could be accomplished through the use of a variety of reducing agents to give $\\beta$-hydroxy phosphonamidates in high yield and high diastereoselectivities.","Thermolysis of the diastereomerically pure $\\beta$-hydroxy phosphonamidates gave a variety of trisubstituted olefins in high yield and very high stereoselectivity. A discussion on anionic mediated olefinations as well as an extension into the stereoselective synthesis of tetrasubstituted olefins is also presented.","Made available in DSpace on 2014-12-17T21:29:13Z (GMT). No. of bitstreams: 1 9503130.pdf: 9529588 bytes, checksum: eda802fe2c5b3f891f436a6e4575a1b1 (MD5) Previous issue date: 1994","Embargo set by: Seth Robbins for item 72462 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","263 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1994."]},{"key":"dc:title","label":"Title","values":["Stereoselective Synthesis of Trisubstituted Olefins"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E."],"dc:creator":["Amburgey, Jack S."],"dc:date":["2014-12-17T21:29:13Z","10000-01-01","1994"],"dc:description":["A new method for the highly stereoselective synthesis of trisubstituted olefins is presented. The method involves the stereoselective construction of various $\\beta$-hydroxy phosphonamidates followed by their thermolysis to provide trisubstituted olefins in extremely high geometrical purity ($&gt;$99/1).","The stereoselective construction of $\\beta$-hydroxy phosphonamidates could be accomplished through three main synthetic transformations. The first involves the acylation of various parent 1,3,2-oxazaphospholidines to provide monoalkylated $\\beta$-keto phosphonamidates in good yield. The second step is the alkylation of the $\\beta$-keto phosphonamidates to provide $\\alpha,\\alpha$-dialkylated $\\beta$-keto phosphonamidates in high yield and very high diastereoselectivities. Finally, the highly diastereoselective reduction of the dialkylated $\\beta$-keto phosphonamidates could be accomplished through the use of a variety of reducing agents to give $\\beta$-hydroxy phosphonamidates in high yield and high diastereoselectivities.","Thermolysis of the diastereomerically pure $\\beta$-hydroxy phosphonamidates gave a variety of trisubstituted olefins in high yield and very high stereoselectivity. A discussion on anionic mediated olefinations as well as an extension into the stereoselective synthesis of tetrasubstituted olefins is also presented.","Made available in DSpace on 2014-12-17T21:29:13Z (GMT). No. of bitstreams: 1 9503130.pdf: 9529588 bytes, checksum: eda802fe2c5b3f891f436a6e4575a1b1 (MD5) Previous issue date: 1994","Embargo set by: Seth Robbins for item 72462 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","263 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1994."],"dc:identifier":["http://hdl.handle.net/2142/72294","(UMI)AAI9503130"],"dc:subject":["Chemistry, Organic"],"dc:title":["Stereoselective Synthesis of Trisubstituted Olefins"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:06Z"}