{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:59426"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:59426","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Asymmetrische Synthese von Gamma-Hydroxy-Alpha-Aminosäuren, 1,3-Aminoalkoholen und 2-Amino-3-Phosphonopropionsäure","abstract":"In this thesis we optimised a procedure to synthesize 1,3-amino alcohols and applied it to a wide range of substituted substrates. Starting from aldehyde SAMP-hydrazones we obtained beta-hydroxy SAMP-hydrazones in a titanium-mediated aza-analogous aldol reaction. After protection, 1,2-addition and cleavage of the chiral auxiliary the products could be isolated over five steps in 30 to 54% overall yield and diastereomeric excesses of 78 to 84% and enantiomeric excesses over 96%. Furthermore we developed a hydrazone Strecker-method for the asymmetric synthesis of alpha-amino acids. The method was tested by the synthesis of six examples, including 2-amino-3-phosphonopropionic acid. The first step was the addition of TMSCN to SAMP-hydrazones to obtain hydrazino nitriles. After protection with Moc-Cl and N-N-bound cleavage with MMPP the resulting protected amino nitriles were easily converted into alpha-amino acids by acidic hydrolysis of the nitrile group under concurrent deprotection. The alpha-amino acids were synthesized in four steps in 10 to 50% overall yield. The enantiomeric excesses of 94 to 97% were determined on the diasteriomeric excesses of the Mosher-amides. We established the absolute configuration by comparison of the NMR-spektra of the Mosher-amides with the spectra of the Mosher-amide of a 1 : 2 induced sample of the purchasable alpha-amino butanoic acid. The combination of several known methods and their optimisation gave us the possibility to synthesize gamma-hydroxy alpha-amino acids in a highly diastereo- und enantioselective manner. This pathway has only slight differences to that used for the synthesis of 1,3-amino alcolhols. In the 1,2-addition we added ceriumfuryl to the C=N-double bound of the hydrazones. After cleavage of the chiral auxiliary the following ozonolysis resulted in gamma-hydroxy alpha-amino acids after six steps in 21 to 27% overall yield. The diastereo- und enantiomeric exesses were higher 96%. 1,3-Amino alcohols and gamma-hydroxy alpha-amino acids are important building blocks in the synthesis of natural products with biological activity.","abstract_html":"In this thesis we optimised a procedure to synthesize 1,3-amino alcohols and applied it to a wide range of substituted substrates. Starting from aldehyde SAMP-hydrazones we obtained beta-hydroxy SAMP-hydrazones in a titanium-mediated aza-analogous aldol reaction. After protection, 1,2-addition and cleavage of the chiral auxiliary the products could be isolated over five steps in 30 to 54% overall yield and diastereomeric excesses of 78 to 84% and enantiomeric excesses over 96%. Furthermore we developed a hydrazone Strecker-method for the asymmetric synthesis of alpha-amino acids. The method was tested by the synthesis of six examples, including 2-amino-3-phosphonopropionic acid. The first step was the addition of TMSCN to SAMP-hydrazones to obtain hydrazino nitriles. After protection with Moc-Cl and N-N-bound cleavage with MMPP the resulting protected amino nitriles were easily converted into alpha-amino acids by acidic hydrolysis of the nitrile group under concurrent deprotection. The alpha-amino acids were synthesized in four steps in 10 to 50% overall yield. The enantiomeric excesses of 94 to 97% were determined on the diasteriomeric excesses of the Mosher-amides. We established the absolute configuration by comparison of the NMR-spektra of the Mosher-amides with the spectra of the Mosher-amide of a 1 : 2 induced sample of the purchasable alpha-amino butanoic acid. The combination of several known methods and their optimisation gave us the possibility to synthesize gamma-hydroxy alpha-amino acids in a highly diastereo- und enantioselective manner. This pathway has only slight differences to that used for the synthesis of 1,3-amino alcolhols. In the 1,2-addition we added ceriumfuryl to the C=N-double bound of the hydrazones. After cleavage of the chiral auxiliary the following ozonolysis resulted in gamma-hydroxy alpha-amino acids after six steps in 21 to 27% overall yield. The diastereo- und enantiomeric exesses were higher 96%. 1,3-Amino alcohols and gamma-hydroxy alpha-amino acids are important building blocks in the synthesis of natural products with biological activity.","abstract_has_math":false,"creators":["Moser, Michael"],"institution":"Publikationsserver der RWTH Aachen University","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Enders, Dieter"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2004,"date_issued":"2004","date_published":"2004","updated_at":"2026-07-30T19:42:39Z","subjects":["info:eu-repo/classification/ddc/540","Alkanolamine","Asymmetrische Synthese","Hydroxyaminosäuren","Alaninderivate","Phosphonogruppe","Chemie"],"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-121213%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121213%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121213%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/59426","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":["Moser, Michael"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:coverage","label":"Dc Coverage","values":["DE"]},{"key":"dc:date","label":"Dc Date","values":["2004"]},{"key":"dc:publisher","label":"Institution","values":["Publikationsserver der RWTH Aachen University"]},{"key":"dc:relation","label":"Dc Relation","values":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-8247"]},{"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","Alkanolamine","Asymmetrische Synthese","Hydroxyaminosäuren","Alaninderivate","Phosphonogruppe","Chemie"]}]},{"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/59426","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121213%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In this thesis we optimised a procedure to synthesize 1,3-amino alcohols and applied it to a wide range of substituted substrates. Starting from aldehyde SAMP-hydrazones we obtained beta-hydroxy SAMP-hydrazones in a titanium-mediated aza-analogous aldol reaction. After protection, 1,2-addition and cleavage of the chiral auxiliary the products could be isolated over five steps in 30 to 54% overall yield and diastereomeric excesses of 78 to 84% and enantiomeric excesses over 96%. Furthermore we developed a hydrazone Strecker-method for the asymmetric synthesis of alpha-amino acids. The method was tested by the synthesis of six examples, including 2-amino-3-phosphonopropionic acid. The first step was the addition of TMSCN to SAMP-hydrazones to obtain hydrazino nitriles. After protection with Moc-Cl and N-N-bound cleavage with MMPP the resulting protected amino nitriles were easily converted into alpha-amino acids by acidic hydrolysis of the nitrile group under concurrent deprotection. The alpha-amino acids were synthesized in four steps in 10 to 50% overall yield. The enantiomeric excesses of 94 to 97% were determined on the diasteriomeric excesses of the Mosher-amides. We established the absolute configuration by comparison of the NMR-spektra of the Mosher-amides with the spectra of the Mosher-amide of a 1 : 2 induced sample of the purchasable alpha-amino butanoic acid. The combination of several known methods and their optimisation gave us the possibility to synthesize gamma-hydroxy alpha-amino acids in a highly diastereo- und enantioselective manner. This pathway has only slight differences to that used for the synthesis of 1,3-amino alcolhols. In the 1,2-addition we added ceriumfuryl to the C=N-double bound of the hydrazones. After cleavage of the chiral auxiliary the following ozonolysis resulted in gamma-hydroxy alpha-amino acids after six steps in 21 to 27% overall yield. The diastereo- und enantiomeric exesses were higher 96%. 1,3-Amino alcohols and gamma-hydroxy alpha-amino acids are important building blocks in the synthesis of natural products with biological activity."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Publikationsserver der RWTH Aachen University III, 222 S. (2004). = Aachen, Techn. Hochsch., Diss., 2004"]},{"key":"dc:title","label":"Title","values":["Asymmetrische Synthese von Gamma-Hydroxy-Alpha-Aminosäuren, 1,3-Aminoalkoholen und 2-Amino-3-Phosphonopropionsäure"]}]}],"canonical_facts":{"dc:contributor":["Enders, Dieter"],"dc:coverage":["DE"],"dc:creator":["Moser, Michael"],"dc:date":["2004"],"dc:description":["In this thesis we optimised a procedure to synthesize 1,3-amino alcohols and applied it to a wide range of substituted substrates. Starting from aldehyde SAMP-hydrazones we obtained beta-hydroxy SAMP-hydrazones in a titanium-mediated aza-analogous aldol reaction. After protection, 1,2-addition and cleavage of the chiral auxiliary the products could be isolated over five steps in 30 to 54% overall yield and diastereomeric excesses of 78 to 84% and enantiomeric excesses over 96%. Furthermore we developed a hydrazone Strecker-method for the asymmetric synthesis of alpha-amino acids. The method was tested by the synthesis of six examples, including 2-amino-3-phosphonopropionic acid. The first step was the addition of TMSCN to SAMP-hydrazones to obtain hydrazino nitriles. After protection with Moc-Cl and N-N-bound cleavage with MMPP the resulting protected amino nitriles were easily converted into alpha-amino acids by acidic hydrolysis of the nitrile group under concurrent deprotection. The alpha-amino acids were synthesized in four steps in 10 to 50% overall yield. The enantiomeric excesses of 94 to 97% were determined on the diasteriomeric excesses of the Mosher-amides. We established the absolute configuration by comparison of the NMR-spektra of the Mosher-amides with the spectra of the Mosher-amide of a 1 : 2 induced sample of the purchasable alpha-amino butanoic acid. The combination of several known methods and their optimisation gave us the possibility to synthesize gamma-hydroxy alpha-amino acids in a highly diastereo- und enantioselective manner. This pathway has only slight differences to that used for the synthesis of 1,3-amino alcolhols. In the 1,2-addition we added ceriumfuryl to the C=N-double bound of the hydrazones. After cleavage of the chiral auxiliary the following ozonolysis resulted in gamma-hydroxy alpha-amino acids after six steps in 21 to 27% overall yield. The diastereo- und enantiomeric exesses were higher 96%. 1,3-Amino alcohols and gamma-hydroxy alpha-amino acids are important building blocks in the synthesis of natural products with biological activity."],"dc:identifier":["https://publications.rwth-aachen.de/record/59426","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121213%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-8247"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Publikationsserver der RWTH Aachen University III, 222 S. (2004). = Aachen, Techn. Hochsch., Diss., 2004"],"dc:subject":["info:eu-repo/classification/ddc/540","Alkanolamine","Asymmetrische Synthese","Hydroxyaminosäuren","Alaninderivate","Phosphonogruppe","Chemie"],"dc:title":["Asymmetrische Synthese von Gamma-Hydroxy-Alpha-Aminosäuren, 1,3-Aminoalkoholen und 2-Amino-3-Phosphonopropionsäure"],"dc:type":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]},"updated_at":"2026-07-30T19:42:39Z"}