{"id":{"repo_id":"colostate","oai_identifier":"oai:mountainscholar.org:10217/235862"},"canonical_url":"https://search.dev.ndltd.org/etd/colostate/oai:mountainscholar.org:10217/235862","repository":{"repo_id":"colostate","name":"Colorado State University","base_url":"https://api.mountainscholar.org/server/oai/request"},"display":{"title":"The asymmetric synthesis of (2S,3R)-capreomycidine and the total synthesis of capreomycin IB","abstract":"An efficient and asymmetric synthesis of the non-proteinogenic amino acid (2S,3R)-capreomycidine is presented. The synthesis features a novel aluminum enolate-aldimine reaction with a chiral glycinate, which sets both stereocenters. A concise and high-yielding approach to the unnatural amino acid (2S,3S)-β-hydroxyornithine is also reported. The key step in this approach is a boron-mediated aldol reaction with a chiral glycinate. Additionally, the first asymmetric syntheses of α-formylglycine dimethyl and diethyl acetals are described. This two-step approach employs a novel titanium enolate of a chiral glycinate, followed by addition of the requisite trialkyl orthoformate to provide a single diastereomer of the glycinate adduct. Hydrogenolysis provides the optically pure acetal of α-formylglycine. Finally, the total synthesis of capreomyc in IB is described. The synthesis features the incorporation of the previously prepared (2S,3R)-capreomycidine. Additionally, the number of protecting group manipulations required in the synthesis has been greatly reduced by the utilization of asparagine in the peptide preparations as a masked precursor to diaminopropanoic acid. Conversion of the asparagine residue to the diaminopropanoic residue is accomplished by a Hofmann rearrangement.","abstract_html":"An efficient and asymmetric synthesis of the non-proteinogenic amino acid (2S,3R)-capreomycidine is presented. The synthesis features a novel aluminum enolate-aldimine reaction with a chiral glycinate, which sets both stereocenters. A concise and high-yielding approach to the unnatural amino acid (2S,3S)-β-hydroxyornithine is also reported. The key step in this approach is a boron-mediated aldol reaction with a chiral glycinate. Additionally, the first asymmetric syntheses of α-formylglycine dimethyl and diethyl acetals are described. This two-step approach employs a novel titanium enolate of a chiral glycinate, followed by addition of the requisite trialkyl orthoformate to provide a single diastereomer of the glycinate adduct. Hydrogenolysis provides the optically pure acetal of α-formylglycine. Finally, the total synthesis of capreomyc in IB is described. The synthesis features the incorporation of the previously prepared (2S,3R)-capreomycidine. Additionally, the number of protecting group manipulations required in the synthesis has been greatly reduced by the utilization of asparagine in the peptide preparations as a masked precursor to diaminopropanoic acid. Conversion of the asparagine residue to the diaminopropanoic residue is accomplished by a Hofmann rearrangement.","abstract_has_math":false,"creators":["DeMong, Duane Eugene, author","Williams, Robert M., advisor"],"institution":"Colorado State University. Libraries","degree_name":"Doctor of Philosophy (Ph.D.)","degree_level":"Doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2003,"date_issued":"2003","date_published":"2003","updated_at":"2026-07-27T19:13:18Z","subjects":["Amino acids -- Synthesis"],"languages":["eng","English"],"rights":["Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. 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Additionally, the first asymmetric syntheses of α-formylglycine dimethyl and diethyl acetals are described. This two-step approach employs a novel titanium enolate of a chiral glycinate, followed by addition of the requisite trialkyl orthoformate to provide a single diastereomer of the glycinate adduct. Hydrogenolysis provides the optically pure acetal of α-formylglycine. Finally, the total synthesis of capreomyc in IB is described. The synthesis features the incorporation of the previously prepared (2S,3R)-capreomycidine. Additionally, the number of protecting group manipulations required in the synthesis has been greatly reduced by the utilization of asparagine in the peptide preparations as a masked precursor to diaminopropanoic acid. Conversion of the asparagine residue to the diaminopropanoic residue is accomplished by a Hofmann rearrangement."]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["doctoral dissertations"]},{"key":"dc:title","label":"Title","values":["The asymmetric synthesis of (2S,3R)-capreomycidine and the total synthesis of capreomycin IB"]}]}],"canonical_facts":{"dc:creator":["DeMong, Duane Eugene, author","Williams, Robert M., advisor"],"dc:date.accessioned":["2022-11-28T17:46:50Z"],"dc:date.available":["2022-11-28T17:46:50Z"],"dc:date.issued":["2003"],"dc:description.abstract":["An efficient and asymmetric synthesis of the non-proteinogenic amino acid (2S,3R)-capreomycidine is presented. The synthesis features a novel aluminum enolate-aldimine reaction with a chiral glycinate, which sets both stereocenters. A concise and high-yielding approach to the unnatural amino acid (2S,3S)-β-hydroxyornithine is also reported. The key step in this approach is a boron-mediated aldol reaction with a chiral glycinate. Additionally, the first asymmetric syntheses of α-formylglycine dimethyl and diethyl acetals are described. This two-step approach employs a novel titanium enolate of a chiral glycinate, followed by addition of the requisite trialkyl orthoformate to provide a single diastereomer of the glycinate adduct. Hydrogenolysis provides the optically pure acetal of α-formylglycine. Finally, the total synthesis of capreomyc in IB is described. The synthesis features the incorporation of the previously prepared (2S,3R)-capreomycidine. Additionally, the number of protecting group manipulations required in the synthesis has been greatly reduced by the utilization of asparagine in the peptide preparations as a masked precursor to diaminopropanoic acid. Conversion of the asparagine residue to the diaminopropanoic residue is accomplished by a Hofmann rearrangement."],"dc:format.medium":["doctoral dissertations"],"dc:identifier.uri":["https://hdl.handle.net/10217/235862","https://doi.org/10.25675/3.018852"],"dc:language":["English"],"dc:language.iso":["eng"],"dc:publisher":["Colorado State University. Libraries"],"dc:relation":["Catalog record number (MMS ID): 991018481299703361","QD431.D45 2003"],"dc:rights":["Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. 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