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Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta

Leone-Stumpf, Danielle

German Title: Synthese und Chromatographie von [RuCp]+-markierten Diarylether Peptoiden als Vorstuffen der Bastadine aus dem Meeresschwamm Ianthella basta

English Title: Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta

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Translation of abstract (English)

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.

Item Type: Dissertation
Supervisor: Lindel, Prof. Dr. Thomas
Date of thesis defense: 20. November 2001
Date Deposited: 17. Jan 2002 00:00
Date: 2001
Faculties / Institutes: The Faculty of Bio Sciences > Institute of Pharmacy and Molecular Biotechnology
Subjects: 610 Medical sciences Medicine
Uncontrolled Keywords: aminopropyl silica , diaryl ethers , marine natural products , peptide labelling , ruthenium sandwich complexes
Additional Information: Teile in: Chem. Eur. J. 2001, 7, 3961-3965
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