{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:61623"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:61623","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Asymmetrische Synthese von 1,3-Aminoalkoholen und deren Anwendung zur Synthese von Azetidinen und 1-Azabicyclen","abstract":"The focus of this thesis work is the asymmetric synthesis of N,O-protected 1,3-aminoalcohols using SAMP/RAMP Hydrazones and their application in asymmetric synthesis. Furthermore, the asymmetric synthesis of 2-substituted azetidines was developed. - Asymmetric synthesis of 1,3-aminoalcoholsA flexible diastereo- and enantioselective synthesis of N,O-protected 1,3-aminoalcohols was developed. In a three step synthesis, first the N,O-protected 1,3-aminoalcohols were synthesized using a nucleophilic 1,2-addition to the C=N-double bond of the SAMP/RAMP hydrazones with organolithium- or organocer-reagents. Second, an epimerization-free reductive N,N-bond-claverage with BH3-THF-complex was performed. Lastly, N-protection with chloroformic acid benzyl ester or tosylchloride afforded the benzylcarbamates or tosylamides, respectively, in overall yields of 22 to 69%. Importantly, the products were formed in high enantio- and diastereomeric purities (ee, de >= 89–96%). - Synthesis of 2-substituted azetidines using activated leaving groups Extending the previous work of J.H. Kirchhoff, 2-substituted azetidines were synthesized using activated leaving group. The 1,3-aminoalcohols, whose amine and alcohol groups were benzylcarbamate and silyl protected, respectively, were first de-silylated. Conversion of the free alcohol to iodide or tosylate afforded the azetidine precursors. Cyclization gave the desired 2-substituted azetidines in 38 to 50% yields over three steps in excellent enantiomeric purities (ee >= 96%). - Synthesis of 2-substituted azetidines under Mitsunobu conditions The 1,3-aminoalcohols, whose amine and alcohol groups were p-tosyl and benzyl protected, respectively, were first de-benzylated with palladium on activated charcoal in methanol. Then, cyclization was effected by treatment with triphenylphosphine and DIAD in THF. The desired 2-substituted azetidines were obtained in 73 to 93% yields over two steps and in excellent enantiomeric excesses (ee >= 96%). Notably, a variety of substituents could be incorporated (n-Bu, t-Bu, n Hexyl, Phenyl, TBSOCH2(CH2)nCH2, n = 1, 2, 3).","abstract_html":"The focus of this thesis work is the asymmetric synthesis of N,O-protected 1,3-aminoalcohols using SAMP/RAMP Hydrazones and their application in asymmetric synthesis. Furthermore, the asymmetric synthesis of 2-substituted azetidines was developed. - Asymmetric synthesis of 1,3-aminoalcoholsA flexible diastereo- and enantioselective synthesis of N,O-protected 1,3-aminoalcohols was developed. In a three step synthesis, first the N,O-protected 1,3-aminoalcohols were synthesized using a nucleophilic 1,2-addition to the C=N-double bond of the SAMP/RAMP hydrazones with organolithium- or organocer-reagents. Second, an epimerization-free reductive N,N-bond-claverage with BH3-THF-complex was performed. Lastly, N-protection with chloroformic acid benzyl ester or tosylchloride afforded the benzylcarbamates or tosylamides, respectively, in overall yields of 22 to 69%. Importantly, the products were formed in high enantio- and diastereomeric purities (ee, de >= 89–96%). - Synthesis of 2-substituted azetidines using activated leaving groups Extending the previous work of J.H. Kirchhoff, 2-substituted azetidines were synthesized using activated leaving group. The 1,3-aminoalcohols, whose amine and alcohol groups were benzylcarbamate and silyl protected, respectively, were first de-silylated. Conversion of the free alcohol to iodide or tosylate afforded the azetidine precursors. Cyclization gave the desired 2-substituted azetidines in 38 to 50% yields over three steps in excellent enantiomeric purities (ee >= 96%). - Synthesis of 2-substituted azetidines under Mitsunobu conditions The 1,3-aminoalcohols, whose amine and alcohol groups were p-tosyl and benzyl protected, respectively, were first de-benzylated with palladium on activated charcoal in methanol. Then, cyclization was effected by treatment with triphenylphosphine and DIAD in THF. The desired 2-substituted azetidines were obtained in 73 to 93% yields over two steps and in excellent enantiomeric excesses (ee >= 96%). Notably, a variety of substituents could be incorporated (n-Bu, t-Bu, n Hexyl, Phenyl, TBSOCH2(CH2)nCH2, n = 1, 2, 3).","abstract_has_math":false,"creators":["Kim, Zin Sig"],"institution":"Mainz","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Enders, Dieter"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2007,"date_issued":"2007","date_published":"2007","updated_at":"2026-07-30T19:43:10Z","subjects":["info:eu-repo/classification/ddc/540","Chemie","Asymmetrische Synthese","SAMP","Mitsunobu-Reaktion","Nucleophile Addition","Hydrazone","1,3-Aminoalkohol","Azetidin","1-Azabicyclen","1,3-aminoalcohol","azetidine","1-azabicycles"],"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-123265%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123265%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123265%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/61623","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Enders, Dieter"]},{"key":"dc:creator","label":"Author","values":["Kim, Zin Sig"]}]},{"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/3-86130-553-4","info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-17756"]},{"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","Chemie","Asymmetrische Synthese","SAMP","Mitsunobu-Reaktion","Nucleophile Addition","Hydrazone","1,3-Aminoalkohol","Azetidin","1-Azabicyclen","1,3-aminoalcohol","azetidine","1-azabicycles"]}]},{"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/61623","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123265%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The focus of this thesis work is the asymmetric synthesis of N,O-protected 1,3-aminoalcohols using SAMP/RAMP Hydrazones and their application in asymmetric synthesis. Furthermore, the asymmetric synthesis of 2-substituted azetidines was developed. - Asymmetric synthesis of 1,3-aminoalcoholsA flexible diastereo- and enantioselective synthesis of N,O-protected 1,3-aminoalcohols was developed. In a three step synthesis, first the N,O-protected 1,3-aminoalcohols were synthesized using a nucleophilic 1,2-addition to the C=N-double bond of the SAMP/RAMP hydrazones with organolithium- or organocer-reagents. Second, an epimerization-free reductive N,N-bond-claverage with BH3-THF-complex was performed. Lastly, N-protection with chloroformic acid benzyl ester or tosylchloride afforded the benzylcarbamates or tosylamides, respectively, in overall yields of 22 to 69%. Importantly, the products were formed in high enantio- and diastereomeric purities (ee, de >= 89–96%). - Synthesis of 2-substituted azetidines using activated leaving groups Extending the previous work of J.H. Kirchhoff, 2-substituted azetidines were synthesized using activated leaving group. The 1,3-aminoalcohols, whose amine and alcohol groups were benzylcarbamate and silyl protected, respectively, were first de-silylated. Conversion of the free alcohol to iodide or tosylate afforded the azetidine precursors. Cyclization gave the desired 2-substituted azetidines in 38 to 50% yields over three steps in excellent enantiomeric purities (ee >= 96%). - Synthesis of 2-substituted azetidines under Mitsunobu conditions The 1,3-aminoalcohols, whose amine and alcohol groups were p-tosyl and benzyl protected, respectively, were first de-benzylated with palladium on activated charcoal in methanol. Then, cyclization was effected by treatment with triphenylphosphine and DIAD in THF. The desired 2-substituted azetidines were obtained in 73 to 93% yields over two steps and in excellent enantiomeric excesses (ee >= 96%). Notably, a variety of substituents could be incorporated (n-Bu, t-Bu, n Hexyl, Phenyl, TBSOCH2(CH2)nCH2, n = 1, 2, 3)."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Mainz, Aachener Beiträge zur Chemie 71, II, 190 S. : graph. Darst. (2007). = Zugl.: Aachen, Techn. Hochsch., Diss., 2006"]},{"key":"dc:title","label":"Title","values":["Asymmetrische Synthese von 1,3-Aminoalkoholen und deren Anwendung zur Synthese von Azetidinen und 1-Azabicyclen"]}]}],"canonical_facts":{"dc:contributor":["Enders, Dieter"],"dc:coverage":["DE"],"dc:creator":["Kim, Zin Sig"],"dc:date":["2007"],"dc:description":["The focus of this thesis work is the asymmetric synthesis of N,O-protected 1,3-aminoalcohols using SAMP/RAMP Hydrazones and their application in asymmetric synthesis. Furthermore, the asymmetric synthesis of 2-substituted azetidines was developed. - Asymmetric synthesis of 1,3-aminoalcoholsA flexible diastereo- and enantioselective synthesis of N,O-protected 1,3-aminoalcohols was developed. In a three step synthesis, first the N,O-protected 1,3-aminoalcohols were synthesized using a nucleophilic 1,2-addition to the C=N-double bond of the SAMP/RAMP hydrazones with organolithium- or organocer-reagents. Second, an epimerization-free reductive N,N-bond-claverage with BH3-THF-complex was performed. Lastly, N-protection with chloroformic acid benzyl ester or tosylchloride afforded the benzylcarbamates or tosylamides, respectively, in overall yields of 22 to 69%. Importantly, the products were formed in high enantio- and diastereomeric purities (ee, de >= 89–96%). - Synthesis of 2-substituted azetidines using activated leaving groups Extending the previous work of J.H. Kirchhoff, 2-substituted azetidines were synthesized using activated leaving group. The 1,3-aminoalcohols, whose amine and alcohol groups were benzylcarbamate and silyl protected, respectively, were first de-silylated. Conversion of the free alcohol to iodide or tosylate afforded the azetidine precursors. Cyclization gave the desired 2-substituted azetidines in 38 to 50% yields over three steps in excellent enantiomeric purities (ee >= 96%). - Synthesis of 2-substituted azetidines under Mitsunobu conditions The 1,3-aminoalcohols, whose amine and alcohol groups were p-tosyl and benzyl protected, respectively, were first de-benzylated with palladium on activated charcoal in methanol. Then, cyclization was effected by treatment with triphenylphosphine and DIAD in THF. The desired 2-substituted azetidines were obtained in 73 to 93% yields over two steps and in excellent enantiomeric excesses (ee >= 96%). Notably, a variety of substituents could be incorporated (n-Bu, t-Bu, n Hexyl, Phenyl, TBSOCH2(CH2)nCH2, n = 1, 2, 3)."],"dc:identifier":["https://publications.rwth-aachen.de/record/61623","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123265%22"],"dc:language":["ger"],"dc:publisher":["Mainz"],"dc:relation":["info:eu-repo/semantics/altIdentifier/isbn/3-86130-553-4","info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-17756"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Mainz, Aachener Beiträge zur Chemie 71, II, 190 S. : graph. Darst. (2007). = Zugl.: Aachen, Techn. Hochsch., Diss., 2006"],"dc:subject":["info:eu-repo/classification/ddc/540","Chemie","Asymmetrische Synthese","SAMP","Mitsunobu-Reaktion","Nucleophile Addition","Hydrazone","1,3-Aminoalkohol","Azetidin","1-Azabicyclen","1,3-aminoalcohol","azetidine","1-azabicycles"],"dc:title":["Asymmetrische Synthese von 1,3-Aminoalkoholen und deren Anwendung zur Synthese von Azetidinen und 1-Azabicyclen"],"dc:type":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]},"updated_at":"2026-07-30T19:43:10Z"}