{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23798"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23798","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Beta-lithiations of carboxamides: An investigation of the regio- and stereoselectivity of directed lithiations","abstract":"An investigation of the diastereoselective $\\beta$-metalation and of the structure of a carbanion of a $\\beta$-phenyl tertiary amide has been carried out. The directed metalation has been found to occur with high diastereoselectivity and the resulting carbanion is best described as a pyramidal benzyllithium species based on $\\sp{13}$C NMR evidence.","abstract_html":"An investigation of the diastereoselective <span class=\"etd-inline-math\">&beta;</span>-metalation and of the structure of a carbanion of a <span class=\"etd-inline-math\">&beta;</span>-phenyl tertiary amide has been carried out. The directed metalation has been found to occur with high diastereoselectivity and the resulting carbanion is best described as a pyramidal benzyllithium species based on $\\sp{13}$C NMR evidence.","abstract_has_math":true,"creators":["Lutz, Gary Paul"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry, Organic","degree_department":null,"school":null,"contributors":["Beak, Peter"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T14:27:28Z","date_published":"2011-05-07T14:27:28Z","updated_at":"2026-07-22T22:25:22Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1991 Lutz, Gary Paul"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210904","(UMI)AAI9210904"],"render_values":[{"text":"AAI9210904","href":null,"code":true},{"text":"(UMI)AAI9210904","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23798","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Beak, Peter"]},{"key":"dc:creator","label":"Author","values":["Lutz, Gary Paul"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T14:27:28Z","10000-01-01","1991"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry, Organic"]},{"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"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1991 Lutz, Gary Paul"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210904","(UMI)AAI9210904","http://hdl.handle.net/2142/23798"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["An investigation of the diastereoselective $\\beta$-metalation and of the structure of a carbanion of a $\\beta$-phenyl tertiary amide has been carried out. The directed metalation has been found to occur with high diastereoselectivity and the resulting carbanion is best described as a pyramidal benzyllithium species based on $\\sp{13}$C NMR evidence.","Secondary amides have been shown to act as directing groups for $\\beta$-lithiations, and the dianion homoenolate equivalents have been shown to react with a variety of electrophiles. We have found that the remote metalations can be directed by secondary amides employing several anion stabilizing groups, and the secondary amides can undergo remote metalations when no $\\alpha$-alkyl substituent is present. The rate of the directed deprotonation has been found to be dependent upon the chain length between the amide group and the anion stabilizing group. The investigation of using secondary amides as homoenolate equivalents as well as the potential and limitations of these homoenolate equivalents will be addressed.","Made available in DSpace on 2011-05-07T14:27:28Z (GMT). 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The directed metalation has been found to occur with high diastereoselectivity and the resulting carbanion is best described as a pyramidal benzyllithium species based on $\\sp{13}$C NMR evidence.","Secondary amides have been shown to act as directing groups for $\\beta$-lithiations, and the dianion homoenolate equivalents have been shown to react with a variety of electrophiles. We have found that the remote metalations can be directed by secondary amides employing several anion stabilizing groups, and the secondary amides can undergo remote metalations when no $\\alpha$-alkyl substituent is present. The rate of the directed deprotonation has been found to be dependent upon the chain length between the amide group and the anion stabilizing group. The investigation of using secondary amides as homoenolate equivalents as well as the potential and limitations of these homoenolate equivalents will be addressed.","Made available in DSpace on 2011-05-07T14:27:28Z (GMT). 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