{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72290"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72290","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Fundamental and Applied Studies in Asymmetric Catalysis","abstract":"In Part I of this thesis, a new class of optically active heterobimetallic complexes is described. The complexes L*MCl2 (M = Pt(II), Pd(II), L* = C2-symmetric boron containing bisphosphine ligand) and (Rh(cod)(L*)) ClO4 (cod = eta2,eta 2-1,5-cyclooctadiene) were synthesized as templates for asymmetric catalytic reactions that could involve substrate precoordination to a Lewis acidic site remote from the transition metal reaction site. Primary amines were found to bind reversibly via a nitrogen-boron interaction to the free ligands L*. 1H NMR measurements revealed that the binding constant of representative primary amines to L* could be tuned through variation of the electronic properties of the substituents covalently bound to boron.","abstract_html":"In Part I of this thesis, a new class of optically active heterobimetallic complexes is described. The complexes L*MCl2 (M = Pt(II), Pd(II), L* = C2-symmetric boron containing bisphosphine ligand) and (Rh(cod)(L*)) ClO4 (cod = eta2,eta 2-1,5-cyclooctadiene) were synthesized as templates for asymmetric catalytic reactions that could involve substrate precoordination to a Lewis acidic site remote from the transition metal reaction site. Primary amines were found to bind reversibly via a nitrogen-boron interaction to the free ligands L*. 1H NMR measurements revealed that the binding constant of representative primary amines to L* could be tuned through variation of the electronic properties of the substituents covalently bound to boron.","abstract_has_math":false,"creators":["Fields, Lisa Beattie"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Jacobsen, Eric N."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-17T21:29:11Z","date_published":"2014-12-17T21:29:11Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI9411619"],"render_values":[{"text":"(UMI)AAI9411619","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72290","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Jacobsen, Eric N."]},{"key":"dc:creator","label":"Author","values":["Fields, Lisa Beattie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:29:11Z","10000-01-01","1993"]},{"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/2142/72290","(UMI)AAI9411619"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In Part I of this thesis, a new class of optically active heterobimetallic complexes is described. The complexes L*MCl2 (M = Pt(II), Pd(II), L* = C2-symmetric boron containing bisphosphine ligand) and (Rh(cod)(L*)) ClO4 (cod = eta2,eta 2-1,5-cyclooctadiene) were synthesized as templates for asymmetric catalytic reactions that could involve substrate precoordination to a Lewis acidic site remote from the transition metal reaction site. Primary amines were found to bind reversibly via a nitrogen-boron interaction to the free ligands L*. 1H NMR measurements revealed that the binding constant of representative primary amines to L* could be tuned through variation of the electronic properties of the substituents covalently bound to boron.","In Part II, the asymmetric synthesis of S-(+)-ibuprofen is described. The key asymmetry-inducing step was the catalytic epoxidation of 4-isobutylstyrene using household bleach as the terminal oxidant and chloro- (S,S)-[(2,2 '-((1,2-diphenyl-1,2-ethanediyl)bis(nitrilomethylidyne)) bis (6-(1,1-dimethylethyl)-4-methylphenolato))-N,N ', O,O'] manganese(III) as the catalyst. Enantioselectivities in the range of 50-63% were obtained using this or similar catalysts. The final product was obtained from the epoxide via treatment with trimethylaluminum followed by KMnO 4 oxidation.","In Part III, the use of chiral Mn(III)salen complexes as asymmetric C-H activation catalysts for aryl alkanes was examined. Indanol was obtained from indan in 23% ee using household bleach as the terminal oxidant. Kinetic resolution of benzylic alcohols also occurred under reaction conditions, with enantioselectivities in the range of 2--20%.","Made available in DSpace on 2014-12-17T21:29:11Z (GMT). No. of bitstreams: 1 9411619.pdf: 4392942 bytes, checksum: a90d7e1d97d91247709ca4d3f273aac0 (MD5) Previous issue date: 1993","Embargo set by: Seth Robbins for item 72458 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","118 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993."]},{"key":"dc:title","label":"Title","values":["Fundamental and Applied Studies in Asymmetric Catalysis"]}]}],"canonical_facts":{"dc:contributor":["Jacobsen, Eric N."],"dc:creator":["Fields, Lisa Beattie"],"dc:date":["2014-12-17T21:29:11Z","10000-01-01","1993"],"dc:description":["In Part I of this thesis, a new class of optically active heterobimetallic complexes is described. The complexes L*MCl2 (M = Pt(II), Pd(II), L* = C2-symmetric boron containing bisphosphine ligand) and (Rh(cod)(L*)) ClO4 (cod = eta2,eta 2-1,5-cyclooctadiene) were synthesized as templates for asymmetric catalytic reactions that could involve substrate precoordination to a Lewis acidic site remote from the transition metal reaction site. Primary amines were found to bind reversibly via a nitrogen-boron interaction to the free ligands L*. 1H NMR measurements revealed that the binding constant of representative primary amines to L* could be tuned through variation of the electronic properties of the substituents covalently bound to boron.","In Part II, the asymmetric synthesis of S-(+)-ibuprofen is described. The key asymmetry-inducing step was the catalytic epoxidation of 4-isobutylstyrene using household bleach as the terminal oxidant and chloro- (S,S)-[(2,2 '-((1,2-diphenyl-1,2-ethanediyl)bis(nitrilomethylidyne)) bis (6-(1,1-dimethylethyl)-4-methylphenolato))-N,N ', O,O'] manganese(III) as the catalyst. Enantioselectivities in the range of 50-63% were obtained using this or similar catalysts. The final product was obtained from the epoxide via treatment with trimethylaluminum followed by KMnO 4 oxidation.","In Part III, the use of chiral Mn(III)salen complexes as asymmetric C-H activation catalysts for aryl alkanes was examined. Indanol was obtained from indan in 23% ee using household bleach as the terminal oxidant. Kinetic resolution of benzylic alcohols also occurred under reaction conditions, with enantioselectivities in the range of 2--20%.","Made available in DSpace on 2014-12-17T21:29:11Z (GMT). No. of bitstreams: 1 9411619.pdf: 4392942 bytes, checksum: a90d7e1d97d91247709ca4d3f273aac0 (MD5) Previous issue date: 1993","Embargo set by: Seth Robbins for item 72458 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","118 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993."],"dc:identifier":["http://hdl.handle.net/2142/72290","(UMI)AAI9411619"],"dc:subject":["Chemistry, Organic"],"dc:title":["Fundamental and Applied Studies in Asymmetric Catalysis"],"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":"2026-07-22T22:26:06Z"}