eprintid: 1842
rev_number: 6
eprint_status: archive
userid: 1
dir: disk0/00/00/18/42
datestamp: 2002-01-17 00:00:00
lastmod: 2014-04-03 11:27:45
status_changed: 2012-08-14 15:02:58
type: doctoralThesis
metadata_visibility: show
creators_name: Leone-Stumpf, Danielle
title: Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta
title_en: Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta
title_de: Synthese und Chromatographie von [RuCp]+-markierten Diarylether Peptoiden als Vorstuffen der Bastadine aus dem Meeresschwamm Ianthella basta
ispublished: pub
subjects: 610
divisions: 160100
adv_faculty: af-14
keywords: aminopropyl silica , diaryl ethers , marine natural products , peptide labelling , ruthenium sandwich complexes
note: Teile in: Chem. Eur. J. 2001, 7, 3961-3965
abstract_translated_text: 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_translated_lang: eng
date: 2001
date_type: published
id_scheme: DOI
id_number: 10.11588/heidok.00001842
ppn_swb: 1643261975
own_urn: urn:nbn:de:bsz:16-opus-18423
date_accepted: 2001-11-20
advisor: HASH(0x564e1c424680)
language: ger
bibsort: LEONESTUMPSYNTHESISA2001
full_text_status: public
citation:   Leone-Stumpf, Danielle  (2001) Synthesis and Chromatography of [RuCp]+-labelled Diaryl Ether Peptoids as Precursors of the Bastadins from the Marine Sponge Ianthella basta.  [Dissertation]     
document_url: https://archiv.ub.uni-heidelberg.de/volltextserver/1842/1/doc.pdf