{"id":{"repo_id":"bologna","oai_identifier":"oai:amsdottorato.cib.unibo.it:1458"},"canonical_url":"https://search.dev.ndltd.org/etd/bologna/oai:amsdottorato.cib.unibo.it:1458","repository":{"repo_id":"bologna","name":"Università di Bologna","base_url":"https://amsdottorato.unibo.it/cgi/oai2"},"display":{"title":"New routes to enantioenriched substances through small organic molecules","abstract":"In this thesis we will disclose the results obtained from the diastereoisomeric salt formation (n salt, p salt and p1,n1 salt) between non-racemic trans-chrysanthemic acid (trans-ChA) and pure enantiomers of threo-2-dimethylamino-1-phenyl-1,3-propanediol (DMPP). The occurrence of p1,n1 salt formation can have profound effects on enantiomer separation of scalemic (non-racemic) mixtures. This phenomenon when accompanied by substrate self-association impedes the complete recovery of the major enantiomer through formation of an inescapable racemate cage. A synthetic sequence for the asymmetric synthesis of bicyclo[3.2.0]heptanones and bicyclo[3.2.0]hept-3-en-6-ones through a cycloaddition strategy is reported. The fundamental step is a [2+2]-cycloaddition of an enantiopure amide derived from the reaction between a set of acids and an oxazolidinone as the chiral auxiliary. The inter- and intramolecular cycloaddition of in situ-generated keteniminium salts gives bicycles with a good enantioselection. A key intermediate of Iloprost, a chemically stable and biologically active mimic of prostacyclin PGI2 is synthesized following a ‘green approach’. An example of simple optical resolution of this racemic intermediate involving the diastereoisomeric salt formation is described.","abstract_html":"In this thesis we will disclose the results obtained from the diastereoisomeric salt formation (n salt, p salt and p1,n1 salt) between non-racemic trans-chrysanthemic acid (trans-ChA) and pure enantiomers of threo-2-dimethylamino-1-phenyl-1,3-propanediol (DMPP). The occurrence of p1,n1 salt formation can have profound effects on enantiomer separation of scalemic (non-racemic) mixtures. This phenomenon when accompanied by substrate self-association impedes the complete recovery of the major enantiomer through formation of an inescapable racemate cage. A synthetic sequence for the asymmetric synthesis of bicyclo[3.2.0]heptanones and bicyclo[3.2.0]hept-3-en-6-ones through a cycloaddition strategy is reported. The fundamental step is a [2+2]-cycloaddition of an enantiopure amide derived from the reaction between a set of acids and an oxazolidinone as the chiral auxiliary. The inter- and intramolecular cycloaddition of in situ-generated keteniminium salts gives bicycles with a good enantioselection. A key intermediate of Iloprost, a chemically stable and biologically active mimic of prostacyclin PGI2 is synthesized following a ‘green approach’. An example of simple optical resolution of this racemic intermediate involving the diastereoisomeric salt formation is described.","abstract_has_math":false,"creators":["Boschi, Francesca <1980>"],"institution":"Alma Mater Studiorum - Università di Bologna","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Righi, Paolo"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-04-27","date_published":"2009-04-27","updated_at":"2026-07-24T01:12:13Z","subjects":["CHIM/06 Chimica organica"],"languages":["en"],"rights":["info:eu-repo/semantics/openAccess"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["urn:nbn:it:unibo-1265"],"render_values":[{"text":"urn:nbn:it:unibo-1265","href":null,"code":true}]}]},"links":{"outbound_url":"https://doi.org/10.6092/unibo/amsdottorato/1458.","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Righi, Paolo"]},{"key":"dc:creator","label":"Author","values":["Boschi, Francesca <1980>"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2009-04-27"]},{"key":"dc:publisher","label":"Institution","values":["Alma Mater Studiorum - Università di Bologna"]},{"key":"dc:relation","label":"Dc Relation","values":["https://amsdottorato.unibo.it/id/eprint/1458/"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral Thesis","PeerReviewed"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["CHIM/06 Chimica organica"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["info:eu-repo/semantics/openAccess"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://amsdottorato.unibo.it/id/eprint/1458/1/Boschi_Francesca_tesi.pdf","urn:nbn:it:unibo-1265","Boschi, Francesca (2009) New routes to enantioenriched substances through small organic molecules, [Dissertation thesis], Alma Mater Studiorum Università di Bologna. 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The fundamental step is a [2+2]-cycloaddition of an enantiopure amide derived from the reaction between a set of acids and an oxazolidinone as the chiral auxiliary. The inter- and intramolecular cycloaddition of in situ-generated keteniminium salts gives bicycles with a good enantioselection. A key intermediate of Iloprost, a chemically stable and biologically active mimic of prostacyclin PGI2 is synthesized following a ‘green approach’. An example of simple optical resolution of this racemic intermediate involving the diastereoisomeric salt formation is described."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["New routes to enantioenriched substances through small organic molecules"]}]}],"canonical_facts":{"dc:contributor":["Righi, Paolo"],"dc:creator":["Boschi, Francesca <1980>"],"dc:date":["2009-04-27"],"dc:description":["In this thesis we will disclose the results obtained from the diastereoisomeric salt formation (n salt, p salt and p1,n1 salt) between non-racemic trans-chrysanthemic acid (trans-ChA) and pure enantiomers of threo-2-dimethylamino-1-phenyl-1,3-propanediol (DMPP). The occurrence of p1,n1 salt formation can have profound effects on enantiomer separation of scalemic (non-racemic) mixtures. This phenomenon when accompanied by substrate self-association impedes the complete recovery of the major enantiomer through formation of an inescapable racemate cage. A synthetic sequence for the asymmetric synthesis of bicyclo[3.2.0]heptanones and bicyclo[3.2.0]hept-3-en-6-ones through a cycloaddition strategy is reported. The fundamental step is a [2+2]-cycloaddition of an enantiopure amide derived from the reaction between a set of acids and an oxazolidinone as the chiral auxiliary. The inter- and intramolecular cycloaddition of in situ-generated keteniminium salts gives bicycles with a good enantioselection. A key intermediate of Iloprost, a chemically stable and biologically active mimic of prostacyclin PGI2 is synthesized following a ‘green approach’. An example of simple optical resolution of this racemic intermediate involving the diastereoisomeric salt formation is described."],"dc:format":["application/pdf"],"dc:identifier":["https://amsdottorato.unibo.it/id/eprint/1458/1/Boschi_Francesca_tesi.pdf","urn:nbn:it:unibo-1265","Boschi, Francesca (2009) New routes to enantioenriched substances through small organic molecules, [Dissertation thesis], Alma Mater Studiorum Università di Bologna. Dottorato di ricerca in Scienze chimiche <https://amsdottorato.unibo.it/view/dottorati/DOT298/>, 21 Ciclo. DOI 10.6092/unibo/amsdottorato/1458."],"dc:language":["en"],"dc:publisher":["Alma Mater Studiorum - Università di Bologna"],"dc:relation":["https://amsdottorato.unibo.it/id/eprint/1458/"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:subject":["CHIM/06 Chimica organica"],"dc:title":["New routes to enantioenriched substances through small organic molecules"],"dc:type":["Doctoral Thesis","PeerReviewed"]},"updated_at":"2026-07-24T01:12:13Z"}