{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:52352"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:52352","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Chirale Sulfonimidamide und Sulfoximine : Synthese, Strukturuntersuchungen und Anwendungen","abstract":"This thesis describes the synthesis and structure determination of chiral sulfur-containing compounds, their use in asymmetric catalysis and the determination of the basicity of a bissulfoximine. In the first part the preparation of enantio- and diastereomerically pure sulfonimidamides bearing either an oxazolidinyl or a cyclohexylamino moiety is described, as well as the synthesis of enantiopure oxazolinyl-derivatized thioureas and one enantiopure oxazolinyl-functionalized guanidine. The structures of the oxazolidinyl-functionalized sulfonimidamides and the oxazolinyl-derivatized thioureas were examined by NMR- and X-ray methods. Furthermore, the first example of an asymmetric metal catalysis using sulfonimidamides as ligands is presented: the cyclohexylamine derived sulfonimidamides were applied in the Cu-catalyzed asymmetric Henry reaction between aromatic aldehydes and nitromethane giving products with enantiomeric excesses up to 95% ee. In the second part of this thesis the basicity of a C2-symmetric naphthaline based bissulfoximine was studied, since this compound shows structural similarities to so-called proton sponges. Protonation experiments towards the determination of the basicity were carried out and the kinetic activity of the bissulfoximine was determined in a proton self-exchange reaction. A discussion of the structures of the free base and the protonated species is done using the data obtained from X-ray analysis. Finally, quantum chemical calculations for the determination of the proton affinity of the bissulfoximine are described.","abstract_html":"This thesis describes the synthesis and structure determination of chiral sulfur-containing compounds, their use in asymmetric catalysis and the determination of the basicity of a bissulfoximine. In the first part the preparation of enantio- and diastereomerically pure sulfonimidamides bearing either an oxazolidinyl or a cyclohexylamino moiety is described, as well as the synthesis of enantiopure oxazolinyl-derivatized thioureas and one enantiopure oxazolinyl-functionalized guanidine. The structures of the oxazolidinyl-functionalized sulfonimidamides and the oxazolinyl-derivatized thioureas were examined by NMR- and X-ray methods. Furthermore, the first example of an asymmetric metal catalysis using sulfonimidamides as ligands is presented: the cyclohexylamine derived sulfonimidamides were applied in the Cu-catalyzed asymmetric Henry reaction between aromatic aldehydes and nitromethane giving products with enantiomeric excesses up to 95% ee. In the second part of this thesis the basicity of a C2-symmetric naphthaline based bissulfoximine was studied, since this compound shows structural similarities to so-called proton sponges. Protonation experiments towards the determination of the basicity were carried out and the kinetic activity of the bissulfoximine was determined in a proton self-exchange reaction. A discussion of the structures of the free base and the protonated species is done using the data obtained from X-ray analysis. Finally, quantum chemical calculations for the determination of the proton affinity of the bissulfoximine are described.","abstract_has_math":false,"creators":["Steurer, Marianne Mette Hoff"],"institution":"Mainz","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Bolm, Carsten"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010","date_published":"2010","updated_at":"2026-07-30T19:40:50Z","subjects":["info:eu-repo/classification/ddc/540","Schwefelorganische Verbindungen","Sulfoximin","Dihydrooxazole","Asymmetrische Synthese","Henry-Reaktion","Protonenschwamm","Chemie","Sulfonimidamid","asymmetrische Katalyse","sulfonimidamide","asymmetric catalysis","sulfur","Henry reaction","proton sponge"],"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-114583%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-114583%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-114583%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/52352","outbound_label":"Repository record","outbound_source":"dc:identifier"},"source_record":{"url":"https://publications.rwth-aachen.de/oai2d?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai%3Apublications.rwth-aachen.de%3A52352","prefix":"oai_dc"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Bolm, Carsten"]},{"key":"dc:creator","label":"Author","values":["Steurer, Marianne Mette Hoff"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:coverage","label":"Dc Coverage","values":["DE"]},{"key":"dc:date","label":"Dc Date","values":["2010"]},{"key":"dc:publisher","label":"Institution","values":["Mainz"]},{"key":"dc:relation","label":"Dc Relation","values":["info:eu-repo/semantics/altIdentifier/isbn/3-86130-620-4","info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-33179"]},{"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","Schwefelorganische Verbindungen","Sulfoximin","Dihydrooxazole","Asymmetrische Synthese","Henry-Reaktion","Protonenschwamm","Chemie","Sulfonimidamid","asymmetrische Katalyse","sulfonimidamide","asymmetric catalysis","sulfur","Henry reaction","proton sponge"]}]},{"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/52352","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-114583%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This thesis describes the synthesis and structure determination of chiral sulfur-containing compounds, their use in asymmetric catalysis and the determination of the basicity of a bissulfoximine. In the first part the preparation of enantio- and diastereomerically pure sulfonimidamides bearing either an oxazolidinyl or a cyclohexylamino moiety is described, as well as the synthesis of enantiopure oxazolinyl-derivatized thioureas and one enantiopure oxazolinyl-functionalized guanidine. The structures of the oxazolidinyl-functionalized sulfonimidamides and the oxazolinyl-derivatized thioureas were examined by NMR- and X-ray methods. Furthermore, the first example of an asymmetric metal catalysis using sulfonimidamides as ligands is presented: the cyclohexylamine derived sulfonimidamides were applied in the Cu-catalyzed asymmetric Henry reaction between aromatic aldehydes and nitromethane giving products with enantiomeric excesses up to 95% ee. In the second part of this thesis the basicity of a C2-symmetric naphthaline based bissulfoximine was studied, since this compound shows structural similarities to so-called proton sponges. Protonation experiments towards the determination of the basicity were carried out and the kinetic activity of the bissulfoximine was determined in a proton self-exchange reaction. A discussion of the structures of the free base and the protonated species is done using the data obtained from X-ray analysis. Finally, quantum chemical calculations for the determination of the proton affinity of the bissulfoximine are described."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Mainz, Aachener Beiträge zur Chemie 95, II, 195 S. : graph. Darst. (2010). = Zugl.: Aachen, Techn. 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Furthermore, the first example of an asymmetric metal catalysis using sulfonimidamides as ligands is presented: the cyclohexylamine derived sulfonimidamides were applied in the Cu-catalyzed asymmetric Henry reaction between aromatic aldehydes and nitromethane giving products with enantiomeric excesses up to 95% ee. In the second part of this thesis the basicity of a C2-symmetric naphthaline based bissulfoximine was studied, since this compound shows structural similarities to so-called proton sponges. Protonation experiments towards the determination of the basicity were carried out and the kinetic activity of the bissulfoximine was determined in a proton self-exchange reaction. A discussion of the structures of the free base and the protonated species is done using the data obtained from X-ray analysis. Finally, quantum chemical calculations for the determination of the proton affinity of the bissulfoximine are described."],"dc:identifier":["https://publications.rwth-aachen.de/record/52352","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-114583%22"],"dc:language":["ger"],"dc:publisher":["Mainz"],"dc:relation":["info:eu-repo/semantics/altIdentifier/isbn/3-86130-620-4","info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-33179"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Mainz, Aachener Beiträge zur Chemie 95, II, 195 S. : graph. Darst. (2010). = Zugl.: Aachen, Techn. 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