{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70391"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70391","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Phosphorus-Stabilized, Carbanion-Accelerated Claisen Rearrangements: Asymmetric Induction via 1,3,2-Oxazaphosphorinanes","abstract":"The carbanion-accelerated Claisen rearrangement has been extended to include phosphorus carbanion-stabilizing groups. The appropriately substituted allyl vinyl ethers are synthesized by the nucleophilic addition of allyloxides to phosphorus-substituted allenes, which are obtained in one step from simple starting materials. The phosphorus-stabilized, carbanion-accelerated Claisen rearrangements proceed rapidly at room temperature in high yield, and the rearrangements are regiospecific and highly stereoselective. Most importantly, the first examples of asymmetric induction in the Claisen rearrangement with chiral phosphorus anion-stabilizing groups are documented. The observed asymmetric induction, which is highly dependent on the metal counterion involved, is explained in terms of both internal and relative diastereoselectivity. The sense of asymmetric induction is established by degradation of the Claisen rearrangement products to ($R$)- and ($S$)-dimethyl methylsuccinates. Two limiting transition state models are proposed to rationalize the high levels of observed diastereoselectivity.","abstract_html":"The carbanion-accelerated Claisen rearrangement has been extended to include phosphorus carbanion-stabilizing groups. The appropriately substituted allyl vinyl ethers are synthesized by the nucleophilic addition of allyloxides to phosphorus-substituted allenes, which are obtained in one step from simple starting materials. The phosphorus-stabilized, carbanion-accelerated Claisen rearrangements proceed rapidly at room temperature in high yield, and the rearrangements are regiospecific and highly stereoselective. Most importantly, the first examples of asymmetric induction in the Claisen rearrangement with chiral phosphorus anion-stabilizing groups are documented. The observed asymmetric induction, which is highly dependent on the metal counterion involved, is explained in terms of both internal and relative diastereoselectivity. The sense of asymmetric induction is established by degradation of the Claisen rearrangement products to ($R$)- and ($S$)-dimethyl methylsuccinates. Two limiting transition state models are proposed to rationalize the high levels of observed diastereoselectivity.","abstract_has_math":true,"creators":["Marlin, John Emory, II"],"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":1987,"date_issued":"1987","date_published":"1987","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8803127"],"render_values":[{"text":"(UMI)AAI8803127","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70391","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":["Marlin, John Emory, II"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1987","2014-12-15T23:19:08Z","10000-01-01"]},{"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/2142/70391","(UMI)AAI8803127"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The carbanion-accelerated Claisen rearrangement has been extended to include phosphorus carbanion-stabilizing groups. The appropriately substituted allyl vinyl ethers are synthesized by the nucleophilic addition of allyloxides to phosphorus-substituted allenes, which are obtained in one step from simple starting materials. The phosphorus-stabilized, carbanion-accelerated Claisen rearrangements proceed rapidly at room temperature in high yield, and the rearrangements are regiospecific and highly stereoselective. Most importantly, the first examples of asymmetric induction in the Claisen rearrangement with chiral phosphorus anion-stabilizing groups are documented. The observed asymmetric induction, which is highly dependent on the metal counterion involved, is explained in terms of both internal and relative diastereoselectivity. The sense of asymmetric induction is established by degradation of the Claisen rearrangement products to ($R$)- and ($S$)-dimethyl methylsuccinates. Two limiting transition state models are proposed to rationalize the high levels of observed diastereoselectivity.","Methods of cleaving the phosphorus-carbon bond are examined. Phosphorus-carbon bond cleavage is observed only under harshly acidic conditions.","Made available in DSpace on 2014-12-15T23:19:08Z (GMT). No. of bitstreams: 1 8803127.pdf: 4718832 bytes, checksum: a77dffbb962a08011751b1f0166d2da7 (MD5) Previous issue date: 1987","Embargo set by: Seth Robbins for item 70557 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","154 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987."]},{"key":"dc:title","label":"Title","values":["Phosphorus-Stabilized, Carbanion-Accelerated Claisen Rearrangements: Asymmetric Induction via 1,3,2-Oxazaphosphorinanes"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E."],"dc:creator":["Marlin, John Emory, II"],"dc:date":["1987","2014-12-15T23:19:08Z","10000-01-01"],"dc:description":["The carbanion-accelerated Claisen rearrangement has been extended to include phosphorus carbanion-stabilizing groups. The appropriately substituted allyl vinyl ethers are synthesized by the nucleophilic addition of allyloxides to phosphorus-substituted allenes, which are obtained in one step from simple starting materials. The phosphorus-stabilized, carbanion-accelerated Claisen rearrangements proceed rapidly at room temperature in high yield, and the rearrangements are regiospecific and highly stereoselective. Most importantly, the first examples of asymmetric induction in the Claisen rearrangement with chiral phosphorus anion-stabilizing groups are documented. The observed asymmetric induction, which is highly dependent on the metal counterion involved, is explained in terms of both internal and relative diastereoselectivity. The sense of asymmetric induction is established by degradation of the Claisen rearrangement products to ($R$)- and ($S$)-dimethyl methylsuccinates. Two limiting transition state models are proposed to rationalize the high levels of observed diastereoselectivity.","Methods of cleaving the phosphorus-carbon bond are examined. Phosphorus-carbon bond cleavage is observed only under harshly acidic conditions.","Made available in DSpace on 2014-12-15T23:19:08Z (GMT). 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