{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84479"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84479","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"(--)-Sparteine Mediated Asymmetric Synthesis Through Conjugate Addition of Allylic and Benzylic Organolithium Species: Development of a Methodology and Its Application Toward a Total Synthesis","abstract":"The synthetic utility of the methodology is demonstrated with the synthesis of diastereo-, and enantiomerically pure 2,3,4-trisubstituted gamma-lactams in high yield. In addition, conjugate addition of the allylic organolithium species with N-protected 4-pyridones provides high yields of the corresponding 1,4-addition adduct with high enantiomeric ratios (ers). The reaction is believed to proceed through an N-acyl pyridinium salt formed on reaction of N-protected pyridone with TMSCl. An organolithium species derived from N-Boc-N-( p-Methoxyphenyl)dimethylphenylsilyl-allylamine, stabilized with a silyl group rather than a phenyl, has been successfully employed in this lithiation-conjugate addition sequence. The enantioenriched products that arise on electrophilic substitution with N-protected pyridones are precursors to piperidine alkaloids. Moreover, this reaction has been applied as the key step in the total synthesis of an immediate precursor to the indolizidine alkaloid castanospermine.","abstract_html":"The synthetic utility of the methodology is demonstrated with the synthesis of diastereo-, and enantiomerically pure 2,3,4-trisubstituted gamma-lactams in high yield. In addition, conjugate addition of the allylic organolithium species with N-protected 4-pyridones provides high yields of the corresponding 1,4-addition adduct with high enantiomeric ratios (ers). The reaction is believed to proceed through an N-acyl pyridinium salt formed on reaction of N-protected pyridone with TMSCl. An organolithium species derived from N-Boc-N-( p-Methoxyphenyl)dimethylphenylsilyl-allylamine, stabilized with a silyl group rather than a phenyl, has been successfully employed in this lithiation-conjugate addition sequence. The enantioenriched products that arise on electrophilic substitution with N-protected pyridones are precursors to piperidine alkaloids. Moreover, this reaction has been applied as the key step in the total synthesis of an immediate precursor to the indolizidine alkaloid castanospermine.","abstract_has_math":false,"creators":["Curtis, Michael David"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Beak, Peter"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:44Z","date_published":"2015-09-25T22:14:44Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9989975"],"render_values":[{"text":"(MiAaPQ)AAI9989975","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84479","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":["Curtis, Michael David"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:44Z","10000-01-01","2000"]},{"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/2142/84479","(MiAaPQ)AAI9989975"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The synthetic utility of the methodology is demonstrated with the synthesis of diastereo-, and enantiomerically pure 2,3,4-trisubstituted gamma-lactams in high yield. In addition, conjugate addition of the allylic organolithium species with N-protected 4-pyridones provides high yields of the corresponding 1,4-addition adduct with high enantiomeric ratios (ers). The reaction is believed to proceed through an N-acyl pyridinium salt formed on reaction of N-protected pyridone with TMSCl. An organolithium species derived from N-Boc-N-( p-Methoxyphenyl)dimethylphenylsilyl-allylamine, stabilized with a silyl group rather than a phenyl, has been successfully employed in this lithiation-conjugate addition sequence. The enantioenriched products that arise on electrophilic substitution with N-protected pyridones are precursors to piperidine alkaloids. Moreover, this reaction has been applied as the key step in the total synthesis of an immediate precursor to the indolizidine alkaloid castanospermine.","Made available in DSpace on 2015-09-25T22:14:44Z (GMT). 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In addition, conjugate addition of the allylic organolithium species with N-protected 4-pyridones provides high yields of the corresponding 1,4-addition adduct with high enantiomeric ratios (ers). The reaction is believed to proceed through an N-acyl pyridinium salt formed on reaction of N-protected pyridone with TMSCl. An organolithium species derived from N-Boc-N-( p-Methoxyphenyl)dimethylphenylsilyl-allylamine, stabilized with a silyl group rather than a phenyl, has been successfully employed in this lithiation-conjugate addition sequence. The enantioenriched products that arise on electrophilic substitution with N-protected pyridones are precursors to piperidine alkaloids. Moreover, this reaction has been applied as the key step in the total synthesis of an immediate precursor to the indolizidine alkaloid castanospermine.","Made available in DSpace on 2015-09-25T22:14:44Z (GMT). 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