{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20514"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20514","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Stereoselective alkylations and rearrangements of chiral phosphonic and phosphinic acid derivatives","abstract":"The stereochemical course of carbon migration from phosphorus to nitrogen and oxygen were investigated. Optically active ($\\geq$99.9% e.e.) phosphonic and phosphinic azides were prepared and photolyzed in methanol to effect the phosphorus analogues of the carbonyl-Curtius rearrangement. These studies showed that carbon migration in the phosphinoyl-Curtius rearrangement proceeds with 99% net retention of configuration while the migration in the first example of the phosphonoyl-Curtius rearrangement occurs with 99.4% net retention of configuration.","abstract_html":"The stereochemical course of carbon migration from phosphorus to nitrogen and oxygen were investigated. Optically active ($\\geq$99.9% e.e.) phosphonic and phosphinic azides were prepared and photolyzed in methanol to effect the phosphorus analogues of the carbonyl-Curtius rearrangement. These studies showed that carbon migration in the phosphinoyl-Curtius rearrangement proceeds with 99% net retention of configuration while the migration in the first example of the phosphonoyl-Curtius rearrangement occurs with 99.4% net retention of configuration.","abstract_has_math":true,"creators":["Dorow, Roberta L."],"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":"2011-05-07T12:41:23Z","date_published":"2011-05-07T12:41:23Z","updated_at":"2026-07-22T22:25:16Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1990 Dorow, Roberta L."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9026171","(UMI)AAI9026171"],"render_values":[{"text":"AAI9026171","href":null,"code":true},{"text":"(UMI)AAI9026171","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20514","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":["Dorow, Roberta L."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:41:23Z","10000-01-01","1990"]},{"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 1990 Dorow, Roberta L."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9026171","(UMI)AAI9026171","http://hdl.handle.net/2142/20514"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The stereochemical course of carbon migration from phosphorus to nitrogen and oxygen were investigated. Optically active ($\\geq$99.9% e.e.) phosphonic and phosphinic azides were prepared and photolyzed in methanol to effect the phosphorus analogues of the carbonyl-Curtius rearrangement. These studies showed that carbon migration in the phosphinoyl-Curtius rearrangement proceeds with 99% net retention of configuration while the migration in the first example of the phosphonoyl-Curtius rearrangement occurs with 99.4% net retention of configuration.","The stereoselectivity in the alkylation reactions of various chiral phosphorus-stabilized benzylic carbanions was also examined. Both racemic and scalemic 2-benzyl-1,3,2-oxazaphosphorinane-2-oxides were employed. The effects of solvent, base, additive, and electrophile were studied. The diastereoselectivity of alkylation is dependent on the phosphorus-stabilized carbanion which is used, but high diastereoselectivity (98:2-95:5) was realized.","Multinuclear NMR spectroscopy was used to gain insight into the solution state structure of both symmetrical and unsymmetrical heterocyclic phosphorus-stabilized benzylic carbanions. The spectral data is consistent with a charge-alternating structure that has a planar anionic carbon. Information about the conformation of the anion as well as the ring form was obtained. Much information about the structure of phosphorus-stabilized carbanions was obtained through X-ray crystallographic studies of the first lithiated phosphonoyl-stabilized carbanion.","Made available in DSpace on 2011-05-07T12:41:23Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9026171.pdf: 12647391 bytes, checksum: c3d7dbe1fa46a38ca8a277b09df55c56 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:44:24Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:19:32-05:00 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 alkylations and rearrangements of chiral phosphonic and phosphinic acid derivatives"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E."],"dc:creator":["Dorow, Roberta L."],"dc:date":["2011-05-07T12:41:23Z","10000-01-01","1990"],"dc:description":["The stereochemical course of carbon migration from phosphorus to nitrogen and oxygen were investigated. Optically active ($\\geq$99.9% e.e.) phosphonic and phosphinic azides were prepared and photolyzed in methanol to effect the phosphorus analogues of the carbonyl-Curtius rearrangement. These studies showed that carbon migration in the phosphinoyl-Curtius rearrangement proceeds with 99% net retention of configuration while the migration in the first example of the phosphonoyl-Curtius rearrangement occurs with 99.4% net retention of configuration.","The stereoselectivity in the alkylation reactions of various chiral phosphorus-stabilized benzylic carbanions was also examined. Both racemic and scalemic 2-benzyl-1,3,2-oxazaphosphorinane-2-oxides were employed. The effects of solvent, base, additive, and electrophile were studied. The diastereoselectivity of alkylation is dependent on the phosphorus-stabilized carbanion which is used, but high diastereoselectivity (98:2-95:5) was realized.","Multinuclear NMR spectroscopy was used to gain insight into the solution state structure of both symmetrical and unsymmetrical heterocyclic phosphorus-stabilized benzylic carbanions. The spectral data is consistent with a charge-alternating structure that has a planar anionic carbon. Information about the conformation of the anion as well as the ring form was obtained. Much information about the structure of phosphorus-stabilized carbanions was obtained through X-ray crystallographic studies of the first lithiated phosphonoyl-stabilized carbanion.","Made available in DSpace on 2011-05-07T12:41:23Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9026171.pdf: 12647391 bytes, checksum: c3d7dbe1fa46a38ca8a277b09df55c56 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:44:24Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:19:32-05:00 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":["AAI9026171","(UMI)AAI9026171","http://hdl.handle.net/2142/20514"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Dorow, Roberta L."],"dc:subject":["Chemistry, Organic"],"dc:title":["Stereoselective alkylations and rearrangements of chiral phosphonic and phosphinic acid derivatives"],"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":"2026-07-22T22:25:16Z"}