{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:59133"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:59133","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Asymmetrische Synthese neuer planar- und zentral-chiraler Ferrocenylliganden","abstract":"In this thesis we describe the enantioselective synthesis of mono- and di-ortho-substituted ferrocenyl diketones via our SAMP/RAMP-hydrazone method. Keystep is the stepwise diastereoselective ortho-metalation of 1,1'-bisbenzoylferrocene-bis-SAMP-hydrazone followed by trapping of various types of electrophiles. Within our studies we demonstrate the broad applicability of this method by using alkyl-, silyl-, phosphin- and sulfur electrophiles. We obtained the desired products in very good yields (85 -100%) and high diastereoselectivities (de >= 96%). The monosubstituted bis-SAMP-hydrazones prepared, could either undergo a second diastereoselective ortho-substitution under the same conditions to lead to 2,2'-substituted bis-SAMP-hydrazones or could be cleaved to produce mono-substituted 1,1'-bisbenzoylferrocenes. In case of second substitutions we applied alkylation, silylation, phosphinylation, hydroxyalkylation and sulfenylation rections in good yields (45 - 89%) and high diastereoselectivities (de >= 96%). To obtain the disubstituted diketones, it was necessary to cleave the corresponding SAMP-hydrazones. We obtained the desired products in very good yields (28 - 98%) and high diastereoselectivities (de >= 96%). Furthermore we developed an efficient asymmetric synthesis of planar chiral monosubstituted diferrocenylketones in good yields and excellent enantiomeric exesses employing the SAMP/RAMP hydrazone methodology. These compounds are versatile starting materials for further synthetic transformations. A second diastereoselective ortho-metalation without a further chiral auxiliary led to the planar chiral disubstituted diferrocenyl ketones in moderate to very good yields and moderate to excellent diastereoselectivities. Reduction using a mixed hydride of LAH and AlCl3 led to the mono- and disubstituted diferocenyl methanes without epimerisation in good to excellent yields. The application of these novel compounds as ligands in asymmetric catalysis was investigated in palladium catalyzed cross-coupling of 1-phenylethyl magnesium chloride with vinyl bromide to give 3-phenyl-1-butene in very good yields and excellent enantioselectivities. Partly these are the best results in this reaction ever described in literature.","abstract_html":"In this thesis we describe the enantioselective synthesis of mono- and di-ortho-substituted ferrocenyl diketones via our SAMP/RAMP-hydrazone method. Keystep is the stepwise diastereoselective ortho-metalation of 1,1'-bisbenzoylferrocene-bis-SAMP-hydrazone followed by trapping of various types of electrophiles. Within our studies we demonstrate the broad applicability of this method by using alkyl-, silyl-, phosphin- and sulfur electrophiles. We obtained the desired products in very good yields (85 -100%) and high diastereoselectivities (de >= 96%). The monosubstituted bis-SAMP-hydrazones prepared, could either undergo a second diastereoselective ortho-substitution under the same conditions to lead to 2,2'-substituted bis-SAMP-hydrazones or could be cleaved to produce mono-substituted 1,1'-bisbenzoylferrocenes. In case of second substitutions we applied alkylation, silylation, phosphinylation, hydroxyalkylation and sulfenylation rections in good yields (45 - 89%) and high diastereoselectivities (de >= 96%). To obtain the disubstituted diketones, it was necessary to cleave the corresponding SAMP-hydrazones. We obtained the desired products in very good yields (28 - 98%) and high diastereoselectivities (de >= 96%). Furthermore we developed an efficient asymmetric synthesis of planar chiral monosubstituted diferrocenylketones in good yields and excellent enantiomeric exesses employing the SAMP/RAMP hydrazone methodology. These compounds are versatile starting materials for further synthetic transformations. A second diastereoselective ortho-metalation without a further chiral auxiliary led to the planar chiral disubstituted diferrocenyl ketones in moderate to very good yields and moderate to excellent diastereoselectivities. Reduction using a mixed hydride of LAH and AlCl3 led to the mono- and disubstituted diferocenyl methanes without epimerisation in good to excellent yields. The application of these novel compounds as ligands in asymmetric catalysis was investigated in palladium catalyzed cross-coupling of 1-phenylethyl magnesium chloride with vinyl bromide to give 3-phenyl-1-butene in very good yields and excellent enantioselectivities. 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Keystep is the stepwise diastereoselective ortho-metalation of 1,1'-bisbenzoylferrocene-bis-SAMP-hydrazone followed by trapping of various types of electrophiles. Within our studies we demonstrate the broad applicability of this method by using alkyl-, silyl-, phosphin- and sulfur electrophiles. We obtained the desired products in very good yields (85 -100%) and high diastereoselectivities (de >= 96%). The monosubstituted bis-SAMP-hydrazones prepared, could either undergo a second diastereoselective ortho-substitution under the same conditions to lead to 2,2'-substituted bis-SAMP-hydrazones or could be cleaved to produce mono-substituted 1,1'-bisbenzoylferrocenes. In case of second substitutions we applied alkylation, silylation, phosphinylation, hydroxyalkylation and sulfenylation rections in good yields (45 - 89%) and high diastereoselectivities (de >= 96%). To obtain the disubstituted diketones, it was necessary to cleave the corresponding SAMP-hydrazones. We obtained the desired products in very good yields (28 - 98%) and high diastereoselectivities (de >= 96%). Furthermore we developed an efficient asymmetric synthesis of planar chiral monosubstituted diferrocenylketones in good yields and excellent enantiomeric exesses employing the SAMP/RAMP hydrazone methodology. These compounds are versatile starting materials for further synthetic transformations. A second diastereoselective ortho-metalation without a further chiral auxiliary led to the planar chiral disubstituted diferrocenyl ketones in moderate to very good yields and moderate to excellent diastereoselectivities. Reduction using a mixed hydride of LAH and AlCl3 led to the mono- and disubstituted diferocenyl methanes without epimerisation in good to excellent yields. The application of these novel compounds as ligands in asymmetric catalysis was investigated in palladium catalyzed cross-coupling of 1-phenylethyl magnesium chloride with vinyl bromide to give 3-phenyl-1-butene in very good yields and excellent enantioselectivities. Partly these are the best results in this reaction ever described in literature."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Publikationsserver der RWTH Aachen University III, 271 S. (2003). = Aachen, Techn. Hochsch., Diss., 2003"]},{"key":"dc:title","label":"Title","values":["Asymmetrische Synthese neuer planar- und zentral-chiraler Ferrocenylliganden"]}]}],"canonical_facts":{"dc:contributor":["Enders, Dieter"],"dc:coverage":["DE"],"dc:creator":["Klumpen, Thomas"],"dc:date":["2003"],"dc:description":["In this thesis we describe the enantioselective synthesis of mono- and di-ortho-substituted ferrocenyl diketones via our SAMP/RAMP-hydrazone method. Keystep is the stepwise diastereoselective ortho-metalation of 1,1'-bisbenzoylferrocene-bis-SAMP-hydrazone followed by trapping of various types of electrophiles. Within our studies we demonstrate the broad applicability of this method by using alkyl-, silyl-, phosphin- and sulfur electrophiles. We obtained the desired products in very good yields (85 -100%) and high diastereoselectivities (de >= 96%). The monosubstituted bis-SAMP-hydrazones prepared, could either undergo a second diastereoselective ortho-substitution under the same conditions to lead to 2,2'-substituted bis-SAMP-hydrazones or could be cleaved to produce mono-substituted 1,1'-bisbenzoylferrocenes. In case of second substitutions we applied alkylation, silylation, phosphinylation, hydroxyalkylation and sulfenylation rections in good yields (45 - 89%) and high diastereoselectivities (de >= 96%). To obtain the disubstituted diketones, it was necessary to cleave the corresponding SAMP-hydrazones. We obtained the desired products in very good yields (28 - 98%) and high diastereoselectivities (de >= 96%). Furthermore we developed an efficient asymmetric synthesis of planar chiral monosubstituted diferrocenylketones in good yields and excellent enantiomeric exesses employing the SAMP/RAMP hydrazone methodology. These compounds are versatile starting materials for further synthetic transformations. A second diastereoselective ortho-metalation without a further chiral auxiliary led to the planar chiral disubstituted diferrocenyl ketones in moderate to very good yields and moderate to excellent diastereoselectivities. Reduction using a mixed hydride of LAH and AlCl3 led to the mono- and disubstituted diferocenyl methanes without epimerisation in good to excellent yields. The application of these novel compounds as ligands in asymmetric catalysis was investigated in palladium catalyzed cross-coupling of 1-phenylethyl magnesium chloride with vinyl bromide to give 3-phenyl-1-butene in very good yields and excellent enantioselectivities. Partly these are the best results in this reaction ever described in literature."],"dc:identifier":["https://publications.rwth-aachen.de/record/59133","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120944%22"],"dc:language":["ger"],"dc:publisher":["Publikationsserver der RWTH Aachen University"],"dc:relation":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-6737"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Publikationsserver der RWTH Aachen University III, 271 S. (2003). = Aachen, Techn. Hochsch., Diss., 2003"],"dc:subject":["info:eu-repo/classification/ddc/540","Ferrocenderivate","Planare Verbindungen","Chirale Verbindungen","Asymmetrische Synthese","Chemie","Ferrocenylliganden"],"dc:title":["Asymmetrische Synthese neuer planar- und zentral-chiraler Ferrocenylliganden"],"dc:type":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]},"updated_at":"2026-07-30T19:42:31Z"}