{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21803"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21803","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Stereoselective carbon-carbon bond forming reactions using chiral phosphorus(V) compounds and the derived anions","abstract":"C$\\sb2$-Symmetric diamines were synthesized in order to examine carbon-carbon bond forming reactions using chiral auxiliary-based phosphorus reagents. The general utility of these diamines as chiral auxiliaries in the diastereoselective alkylation of P-alkyl anions was examined. A systematic study of the alkylation of the P-alkyl anions was accomplished varying N-alkyl and P-alkyl substituents. High diastereoselectivity was achieved with N-neopentyl substrates (up to 92:8 diastereoselectivity).","abstract_html":"C$\\sb2$-Symmetric diamines were synthesized in order to examine carbon-carbon bond forming reactions using chiral auxiliary-based phosphorus reagents. The general utility of these diamines as chiral auxiliaries in the diastereoselective alkylation of P-alkyl anions was examined. A systematic study of the alkylation of the P-alkyl anions was accomplished varying N-alkyl and P-alkyl substituents. High diastereoselectivity was achieved with N-neopentyl substrates (up to 92:8 diastereoselectivity).","abstract_has_math":true,"creators":["Kim, Jung Ho"],"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":2011,"date_issued":"2011-05-07T13:19:37Z","date_published":"2011-05-07T13:19:37Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1992 Kim, Jung Ho"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236502","(UMI)AAI9236502"],"render_values":[{"text":"AAI9236502","href":null,"code":true},{"text":"(UMI)AAI9236502","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21803","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":["Kim, Jung Ho"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:19:37Z","10000-01-01","1992"]},{"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"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1992 Kim, Jung Ho"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9236502","(UMI)AAI9236502","http://hdl.handle.net/2142/21803"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["C$\\sb2$-Symmetric diamines were synthesized in order to examine carbon-carbon bond forming reactions using chiral auxiliary-based phosphorus reagents. The general utility of these diamines as chiral auxiliaries in the diastereoselective alkylation of P-alkyl anions was examined. A systematic study of the alkylation of the P-alkyl anions was accomplished varying N-alkyl and P-alkyl substituents. High diastereoselectivity was achieved with N-neopentyl substrates (up to 92:8 diastereoselectivity).","The P-allyl anions with varying phosphorus substituents have heen investigated. The diastereoselectivity and the regioselectivity of Michael reactions of chiral cis-oxazaphosphorinanes with cyclic enones were very high. The reaction with chiral trans-oxazaphosphorinanes was not selective. The conjugate addition reaction of a variety of P-allyldiazaphosphorinanes with cyclic enones, varying the substituent of P-allyl unit, was highly regio- and diastereoselective.","The nucleophilic addition to the $\\alpha,\\beta$-unsaturated phosphorus(V) compounds proved to be highly nucleophile-dependent. The nucleophiles with certain range of pK$\\sb{\\rm a}$ values (25-32) have been shown to react with the $\\alpha,\\beta$-unsaturated phosphorus(V) compounds. The diastereoselectivity of the reaction with sulfone stabilized anions or the amide enolates was low in either the internal or relative sense due to the flexible conformation of the P-propenyl side chain.","The general reactivity of P-acyl enolate was extraordinarily low toward usual electrophiles except for silylating agents (TMSCl, TESCl) which produced (E)-silyl enol ethers exclusively. Asymmetric aldol reaction of the enolates derived from P-acylphosphorus heterocycles were not highly successful (up to 36% e.e.) mostly due to their low reactivity and the nature of the thermodynamically controlled reaction.","Made available in DSpace on 2011-05-07T13:19:37Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236502.pdf: 12957399 bytes, checksum: 35212c0f6d7427a422b51c4f58748b6c (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:18Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:38-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Stereoselective carbon-carbon bond forming reactions using chiral phosphorus(V) compounds and the derived anions"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E."],"dc:creator":["Kim, Jung Ho"],"dc:date":["2011-05-07T13:19:37Z","10000-01-01","1992"],"dc:description":["C$\\sb2$-Symmetric diamines were synthesized in order to examine carbon-carbon bond forming reactions using chiral auxiliary-based phosphorus reagents. The general utility of these diamines as chiral auxiliaries in the diastereoselective alkylation of P-alkyl anions was examined. A systematic study of the alkylation of the P-alkyl anions was accomplished varying N-alkyl and P-alkyl substituents. High diastereoselectivity was achieved with N-neopentyl substrates (up to 92:8 diastereoselectivity).","The P-allyl anions with varying phosphorus substituents have heen investigated. The diastereoselectivity and the regioselectivity of Michael reactions of chiral cis-oxazaphosphorinanes with cyclic enones were very high. The reaction with chiral trans-oxazaphosphorinanes was not selective. The conjugate addition reaction of a variety of P-allyldiazaphosphorinanes with cyclic enones, varying the substituent of P-allyl unit, was highly regio- and diastereoselective.","The nucleophilic addition to the $\\alpha,\\beta$-unsaturated phosphorus(V) compounds proved to be highly nucleophile-dependent. The nucleophiles with certain range of pK$\\sb{\\rm a}$ values (25-32) have been shown to react with the $\\alpha,\\beta$-unsaturated phosphorus(V) compounds. The diastereoselectivity of the reaction with sulfone stabilized anions or the amide enolates was low in either the internal or relative sense due to the flexible conformation of the P-propenyl side chain.","The general reactivity of P-acyl enolate was extraordinarily low toward usual electrophiles except for silylating agents (TMSCl, TESCl) which produced (E)-silyl enol ethers exclusively. Asymmetric aldol reaction of the enolates derived from P-acylphosphorus heterocycles were not highly successful (up to 36% e.e.) mostly due to their low reactivity and the nature of the thermodynamically controlled reaction.","Made available in DSpace on 2011-05-07T13:19:37Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9236502.pdf: 12957399 bytes, checksum: 35212c0f6d7427a422b51c4f58748b6c (MD5) Previous issue date: 1992","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:53:18Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:24:38-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9236502","(UMI)AAI9236502","http://hdl.handle.net/2142/21803"],"dc:language":["eng"],"dc:rights":["Copyright 1992 Kim, Jung Ho"],"dc:subject":["Chemistry, Organic"],"dc:title":["Stereoselective carbon-carbon bond forming reactions using chiral phosphorus(V) compounds and the derived anions"],"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":"2026-07-22T22:25:18Z"}