{"id":{"repo_id":"heid-diss","oai_identifier":"oai:archiv.ub.uni-heidelberg.de:1842"},"canonical_url":"https://search.dev.ndltd.org/etd/heid-diss/oai:archiv.ub.uni-heidelberg.de:1842","repository":{"repo_id":"heid-diss","name":"Universität Heidelberg","base_url":"http://archiv.ub.uni-heidelberg.de/volltextserver/cgi/oai2"},"display":{"title":"Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta","abstract":"The bastadins are bromo tyrosine-derived tetrapeptides linked via two diaryl ether and two amide bonds. The synthesis of the ruthenium-labelled peptoids in this thesis uses the nucleophilic attack of phenolates on [RuCp]+-complexed chloroarenes to form diaryl ethers in the preparation of metal-labelled bastadin model compounds. The purification and characterisation of [RuCp]+-labelled peptoids has not, until now, been systematically studied. Despite the attractive properties of ruthenium radioisotopes for diagnostic medicine, uses of the air and water-stable [RuCp]+-labelled amino acids and peptides are very limited. For the first time, aminopropyl silica was employed as stationary phase for the purification and separation of [RuCp]+-complexes, using gradients of iPrOH-CH3CN as mobile phase. This new separation protocol solved also earlier problems including the use of [18]crown-6 with KOtBu as a base and monitoring of the reactions with TLC. Purification of the OH-free dipeptide (northern hemisphere of the bastarane skeleton) on aminopropyl silica showed that this phase is also appropriate for structures bearing an acidic moiety. A critical question concerned the behaviour of ambident nucleophiles simultaneously possessing free amine and free phenol functionalities in the ruthenium-mediated synthesis of diaryl ethers. The results revealed the preference for the phenol as nucleophile, and encouraged the synthesis of the tripeptides. The open-chain bis-[RuCp]+-complexed ABB'A' system is the largest peptoid labelled with two ruthenium moieties. This thesis brought important progress to ruthenium arene chemistry, mainly through: I) use of a base which promotes complete diaryl ether formation; II) monitoring of the reactions with TLC; III) use of the [RuCp]+-complexes in more than one reaction step and IV) preparation and purification of [RuCp]+-complexes as metal-labelled peptoids.","abstract_html":"The bastadins are bromo tyrosine-derived tetrapeptides linked via two diaryl ether and two amide bonds. The synthesis of the ruthenium-labelled peptoids in this thesis uses the nucleophilic attack of phenolates on [RuCp]+-complexed chloroarenes to form diaryl ethers in the preparation of metal-labelled bastadin model compounds. The purification and characterisation of [RuCp]+-labelled peptoids has not, until now, been systematically studied. Despite the attractive properties of ruthenium radioisotopes for diagnostic medicine, uses of the air and water-stable [RuCp]+-labelled amino acids and peptides are very limited. For the first time, aminopropyl silica was employed as stationary phase for the purification and separation of [RuCp]+-complexes, using gradients of iPrOH-CH3CN as mobile phase. This new separation protocol solved also earlier problems including the use of [18]crown-6 with KOtBu as a base and monitoring of the reactions with TLC. Purification of the OH-free dipeptide (northern hemisphere of the bastarane skeleton) on aminopropyl silica showed that this phase is also appropriate for structures bearing an acidic moiety. A critical question concerned the behaviour of ambident nucleophiles simultaneously possessing free amine and free phenol functionalities in the ruthenium-mediated synthesis of diaryl ethers. The results revealed the preference for the phenol as nucleophile, and encouraged the synthesis of the tripeptides. The open-chain bis-[RuCp]+-complexed ABB'A' system is the largest peptoid labelled with two ruthenium moieties. This thesis brought important progress to ruthenium arene chemistry, mainly through: I) use of a base which promotes complete diaryl ether formation; II) monitoring of the reactions with TLC; III) use of the [RuCp]+-complexes in more than one reaction step and IV) preparation and purification of [RuCp]+-complexes as metal-labelled peptoids.","abstract_has_math":false,"creators":["Leone-Stumpf, Danielle"],"institution":"Universität Heidelberg","degree_name":null,"degree_level":"thesis.doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":["Lindel, Thomas"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2001,"date_issued":"2001-11-20","date_published":"2001-11-20","updated_at":"2026-07-24T02:29:09Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://www.ub.uni-heidelberg.de/archiv/1842","outbound_label":"Repository record","outbound_source":"source_url"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Lindel, Thomas"]},{"key":"dc:creator","label":"Author","values":["Leone-Stumpf, Danielle"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:publisher","label":"Institution","values":["Universitätsbibliothek Heidelberg"]},{"key":"dc:type","label":"Dc Type","values":["doctoralThesis"]},{"key":"thesis:degree_level","label":"Degree Level","values":["thesis.doctoral"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Universität Heidelberg"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The bastadins are bromo tyrosine-derived tetrapeptides linked via two diaryl ether and two amide bonds. The synthesis of the ruthenium-labelled peptoids in this thesis uses the nucleophilic attack of phenolates on [RuCp]+-complexed chloroarenes to form diaryl ethers in the preparation of metal-labelled bastadin model compounds. The purification and characterisation of [RuCp]+-labelled peptoids has not, until now, been systematically studied. Despite the attractive properties of ruthenium radioisotopes for diagnostic medicine, uses of the air and water-stable [RuCp]+-labelled amino acids and peptides are very limited. For the first time, aminopropyl silica was employed as stationary phase for the purification and separation of [RuCp]+-complexes, using gradients of iPrOH-CH3CN as mobile phase. This new separation protocol solved also earlier problems including the use of [18]crown-6 with KOtBu as a base and monitoring of the reactions with TLC. Purification of the OH-free dipeptide (northern hemisphere of the bastarane skeleton) on aminopropyl silica showed that this phase is also appropriate for structures bearing an acidic moiety. A critical question concerned the behaviour of ambident nucleophiles simultaneously possessing free amine and free phenol functionalities in the ruthenium-mediated synthesis of diaryl ethers. The results revealed the preference for the phenol as nucleophile, and encouraged the synthesis of the tripeptides. The open-chain bis-[RuCp]+-complexed ABB'A' system is the largest peptoid labelled with two ruthenium moieties. This thesis brought important progress to ruthenium arene chemistry, mainly through: I) use of a base which promotes complete diaryl ether formation; II) monitoring of the reactions with TLC; III) use of the [RuCp]+-complexes in more than one reaction step and IV) preparation and purification of [RuCp]+-complexes as metal-labelled peptoids."]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta","Synthese und Chromatographie von [RuCp]+-markierten Diarylether Peptoiden als Vorstuffen der Bastadine aus dem Meeresschwamm Ianthella basta"]}]}],"canonical_facts":{"dc:contributor":["Lindel, Thomas"],"dc:creator":["Leone-Stumpf, Danielle"],"dc:description.abstract":["The bastadins are bromo tyrosine-derived tetrapeptides linked via two diaryl ether and two amide bonds. The synthesis of the ruthenium-labelled peptoids in this thesis uses the nucleophilic attack of phenolates on [RuCp]+-complexed chloroarenes to form diaryl ethers in the preparation of metal-labelled bastadin model compounds. The purification and characterisation of [RuCp]+-labelled peptoids has not, until now, been systematically studied. Despite the attractive properties of ruthenium radioisotopes for diagnostic medicine, uses of the air and water-stable [RuCp]+-labelled amino acids and peptides are very limited. For the first time, aminopropyl silica was employed as stationary phase for the purification and separation of [RuCp]+-complexes, using gradients of iPrOH-CH3CN as mobile phase. This new separation protocol solved also earlier problems including the use of [18]crown-6 with KOtBu as a base and monitoring of the reactions with TLC. Purification of the OH-free dipeptide (northern hemisphere of the bastarane skeleton) on aminopropyl silica showed that this phase is also appropriate for structures bearing an acidic moiety. A critical question concerned the behaviour of ambident nucleophiles simultaneously possessing free amine and free phenol functionalities in the ruthenium-mediated synthesis of diaryl ethers. The results revealed the preference for the phenol as nucleophile, and encouraged the synthesis of the tripeptides. The open-chain bis-[RuCp]+-complexed ABB'A' system is the largest peptoid labelled with two ruthenium moieties. This thesis brought important progress to ruthenium arene chemistry, mainly through: I) use of a base which promotes complete diaryl ether formation; II) monitoring of the reactions with TLC; III) use of the [RuCp]+-complexes in more than one reaction step and IV) preparation and purification of [RuCp]+-complexes as metal-labelled peptoids."],"dc:format.medium":["application/pdf"],"dc:publisher":["Universitätsbibliothek Heidelberg"],"dc:title":["Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta","Synthese und Chromatographie von [RuCp]+-markierten Diarylether Peptoiden als Vorstuffen der Bastadine aus dem Meeresschwamm Ianthella basta"],"dc:type":["doctoralThesis"],"thesis:degree_level":["thesis.doctoral"],"thesis:institution_name":["Universität Heidelberg"]},"updated_at":"2026-07-24T02:29:09Z"}