{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84258"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84258","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Studies in Asymmetric Catalysis: Lewis Base catalyzed/Lewis Acid Mediated Aldol Reactions of Ketone- and Amide Derived Nucleophiles","abstract":"Additionally, the use of the silicon tetrachloride---chiral phosphoramide system has proven a competent catalyst for highly selective vinylogous aldol reactions between dienolates derived from a variety of alpha,beta-unsaturated carbonyl compounds to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded excellent enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although ketone-derived dienolate did not react with aliphatic aldehydes, amide-derived dienolates were found to undergo addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivity achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride---chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.","abstract_html":"Additionally, the use of the silicon tetrachloride---chiral phosphoramide system has proven a competent catalyst for highly selective vinylogous aldol reactions between dienolates derived from a variety of alpha,beta-unsaturated carbonyl compounds to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded excellent enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although ketone-derived dienolate did not react with aliphatic aldehydes, amide-derived dienolates were found to undergo addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivity achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride---chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.","abstract_has_math":false,"creators":["Heemstra, John Richard, Jr"],"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":"2015-09-25T22:13:41Z","date_published":"2015-09-25T22:13:41Z","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3269914"],"render_values":[{"text":"(MiAaPQ)AAI3269914","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84258","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":["Heemstra, John Richard, Jr"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:13:41Z","10000-01-01","2007"]},{"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/2142/84258","(MiAaPQ)AAI3269914"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Additionally, the use of the silicon tetrachloride---chiral phosphoramide system has proven a competent catalyst for highly selective vinylogous aldol reactions between dienolates derived from a variety of alpha,beta-unsaturated carbonyl compounds to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded excellent enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although ketone-derived dienolate did not react with aliphatic aldehydes, amide-derived dienolates were found to undergo addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivity achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride---chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.","Made available in DSpace on 2015-09-25T22:13:41Z (GMT). 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