{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:62367"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:62367","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Rhodium-katalysierte, asymmetrische Synthese: Ligandendesign und Methodik","abstract":"The development of new and efficient catalysts is of utterly importance for the improvement of existing reactions and the discovery of new catalytic reactions. On the one hand this PhD thesis deals with the synthesis of novel, enantiopure diphosphines and phosphine-olefin-complexes bearing a cyrhetrene backbone, which catalyze various reactions, e.g. the Hayashi-Miyaura-reaction and the hydrogenation of arylenamides, with high selectivities. On the other hand the first asymmetric intermolecular hydroacylation of olefins with salicylaldehydes was developed. A variety of rhodium(I) complexes were examined by in situ preparation from the corresponding catalyst precursors and phosphorous-containing monodentate and bidentate ligands. Application of bidentate ligands such as members of the Taniaphos or the Walphos family furnished the exo-diastereomer predominantly and with up to 82% ee. In contrast, the use of monodentate ligands such as the phosphoramidite MonoPhos™ led diastereoselectively to the endo-diastereomer with up to 54% ee. Initial experiments with bidentate phosphoramidite-phosphite derivatives of hydroxyproline provided promising results, giving the exo-diastereomer predominantly with up to 84% ee.","abstract_html":"The development of new and efficient catalysts is of utterly importance for the improvement of existing reactions and the discovery of new catalytic reactions. On the one hand this PhD thesis deals with the synthesis of novel, enantiopure diphosphines and phosphine-olefin-complexes bearing a cyrhetrene backbone, which catalyze various reactions, e.g. the Hayashi-Miyaura-reaction and the hydrogenation of arylenamides, with high selectivities. On the other hand the first asymmetric intermolecular hydroacylation of olefins with salicylaldehydes was developed. A variety of rhodium(I) complexes were examined by in situ preparation from the corresponding catalyst precursors and phosphorous-containing monodentate and bidentate ligands. Application of bidentate ligands such as members of the Taniaphos or the Walphos family furnished the exo-diastereomer predominantly and with up to 82% ee. In contrast, the use of monodentate ligands such as the phosphoramidite MonoPhos™ led diastereoselectively to the endo-diastereomer with up to 54% ee. Initial experiments with bidentate phosphoramidite-phosphite derivatives of hydroxyproline provided promising results, giving the exo-diastereomer predominantly with up to 84% ee.","abstract_has_math":false,"creators":["Stemmler, René T."],"institution":"Mainz","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Bolm, Carsten"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2007,"date_issued":"2007","date_published":"2007","updated_at":"2026-07-30T19:43:28Z","subjects":["info:eu-repo/classification/ddc/540","Asymmetrische Synthese","Katalyse","Rhodium","Rhenium","Ferrocen","Chemie","Rhodiumkomplexe","Carbonylkomplexe","Cyrhretrene","phosphine","ligand","ketone","1,4-addition"],"languages":["ger"],"rights":["info:eu-repo/semantics/openAccess"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123938%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123938%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123938%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/62367","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Bolm, Carsten"]},{"key":"dc:creator","label":"Author","values":["Stemmler, René T."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:coverage","label":"Dc Coverage","values":["DE"]},{"key":"dc:date","label":"Dc Date","values":["2007"]},{"key":"dc:publisher","label":"Institution","values":["Mainz"]},{"key":"dc:relation","label":"Dc Relation","values":["info:eu-repo/semantics/altIdentifier/isbn/3-86130-561-5","info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-19632"]},{"key":"dc:type","label":"Dc Type","values":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["info:eu-repo/classification/ddc/540","Asymmetrische Synthese","Katalyse","Rhodium","Rhenium","Ferrocen","Chemie","Rhodiumkomplexe","Carbonylkomplexe","Cyrhretrene","phosphine","ligand","ketone","1,4-addition"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["ger"]},{"key":"dc:rights","label":"Dc Rights","values":["info:eu-repo/semantics/openAccess"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://publications.rwth-aachen.de/record/62367","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123938%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The development of new and efficient catalysts is of utterly importance for the improvement of existing reactions and the discovery of new catalytic reactions. On the one hand this PhD thesis deals with the synthesis of novel, enantiopure diphosphines and phosphine-olefin-complexes bearing a cyrhetrene backbone, which catalyze various reactions, e.g. the Hayashi-Miyaura-reaction and the hydrogenation of arylenamides, with high selectivities. On the other hand the first asymmetric intermolecular hydroacylation of olefins with salicylaldehydes was developed. A variety of rhodium(I) complexes were examined by in situ preparation from the corresponding catalyst precursors and phosphorous-containing monodentate and bidentate ligands. Application of bidentate ligands such as members of the Taniaphos or the Walphos family furnished the exo-diastereomer predominantly and with up to 82% ee. In contrast, the use of monodentate ligands such as the phosphoramidite MonoPhos™ led diastereoselectively to the endo-diastereomer with up to 54% ee. Initial experiments with bidentate phosphoramidite-phosphite derivatives of hydroxyproline provided promising results, giving the exo-diastereomer predominantly with up to 84% ee."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Mainz, Aachener Beiträge zur Chemie 79, VI, 203 S. (2007). = Zugl.: Aachen, Techn. Hochsch., Diss., 2007"]},{"key":"dc:title","label":"Title","values":["Rhodium-katalysierte, asymmetrische Synthese: Ligandendesign und Methodik"]}]}],"canonical_facts":{"dc:contributor":["Bolm, Carsten"],"dc:coverage":["DE"],"dc:creator":["Stemmler, René T."],"dc:date":["2007"],"dc:description":["The development of new and efficient catalysts is of utterly importance for the improvement of existing reactions and the discovery of new catalytic reactions. On the one hand this PhD thesis deals with the synthesis of novel, enantiopure diphosphines and phosphine-olefin-complexes bearing a cyrhetrene backbone, which catalyze various reactions, e.g. the Hayashi-Miyaura-reaction and the hydrogenation of arylenamides, with high selectivities. On the other hand the first asymmetric intermolecular hydroacylation of olefins with salicylaldehydes was developed. A variety of rhodium(I) complexes were examined by in situ preparation from the corresponding catalyst precursors and phosphorous-containing monodentate and bidentate ligands. Application of bidentate ligands such as members of the Taniaphos or the Walphos family furnished the exo-diastereomer predominantly and with up to 82% ee. In contrast, the use of monodentate ligands such as the phosphoramidite MonoPhos™ led diastereoselectively to the endo-diastereomer with up to 54% ee. Initial experiments with bidentate phosphoramidite-phosphite derivatives of hydroxyproline provided promising results, giving the exo-diastereomer predominantly with up to 84% ee."],"dc:identifier":["https://publications.rwth-aachen.de/record/62367","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123938%22"],"dc:language":["ger"],"dc:publisher":["Mainz"],"dc:relation":["info:eu-repo/semantics/altIdentifier/isbn/3-86130-561-5","info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-19632"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Mainz, Aachener Beiträge zur Chemie 79, VI, 203 S. (2007). = Zugl.: Aachen, Techn. Hochsch., Diss., 2007"],"dc:subject":["info:eu-repo/classification/ddc/540","Asymmetrische Synthese","Katalyse","Rhodium","Rhenium","Ferrocen","Chemie","Rhodiumkomplexe","Carbonylkomplexe","Cyrhretrene","phosphine","ligand","ketone","1,4-addition"],"dc:title":["Rhodium-katalysierte, asymmetrische Synthese: Ligandendesign und Methodik"],"dc:type":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]},"updated_at":"2026-07-30T19:43:28Z"}