Kompleksi metala d-bloka i konjugata aminokiselina s oksazolinima i trifenilfosfinima kao kiralni katalizatori u reakcijama hidrogenacije

doctoral thesis

• Title (english): D-block metal complexes with amino acid conjugates of oxazolines and triphenylphosphines as chiral catalysts iN hydrogenation reactions
• Author: Marija Bakija
• Mentor: Srećko Kirin (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Marina Šekutor (član povjerenstva)
• Committee member: Mirta Rubčić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2025-01-09, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Pripravljeno je i okarakterizirano 22 aminokiselinska (Ala, Gly, Phe ili Gly-Val-Phe) biokonjugata oksazolina i 5 oksazolina bez aminokiselinskih supstituenata te njihovih metalnih kompleksa (Cd(II), Co(II), Ir(I), Rh(I) i Zn(II)). Ispitan je utjecaj supramolekulskih interakcija na agregaciju monooksazolinskih spojeva nekoordiniranih i koordiniranih s metalom te na selektivnost u enantioselektivnoj hidrogenaciji. Spektroskopskim tehnikama u otopini je potvrđeno da oksazolini s jednim... More tripeptidnim ili dva monopeptidna lanca agregiraju bez metala, dok u svim metalnim kompleksima aminokiselinskih derivata djeluju nekovalentne intramolekulske interakcije. Indukcija kiralnosti na prokiralnom metalu u kompleksima je potvrđena CD spektroskopijom, a kristalne strukture pokazuju da je helikalna kiralnost inducirana kompleksacijom. Sklonost nastajanja agregata nemetaliranih spojeva, te helikalne strukture u metalnim spojevima dodatno su analizirane CREST/CENSO i DFT računalnim metodama. Kompleksi rodija(I) i iridija(I) homo- i hetero-kombinacija aminokiselinskih biokonjugata oksazolina i literaturno poznatog trifenilfosfina s indukcijom kiralnosti upotrijebljeni su u enantioselektivnoj hidrogenaciji derivata metil-(Z)-3-fenilprop-2-enoata, pri čemu je maksimalno dobivena vrijednost enantioselektivnosti 85%. Less

Abstract (english)

A set of 22 oxazoline amino acid bioconjugates (Ala, Gly, Phe and Gly-Val-Phe) and corresponding metal complexes were prepared and characterized (Cd(II), Co(II), Ir(I), Rh(I) i Zn(II)). The influence of supramolecular interactions on the aggregation of non-metallated and metalled mono-oxazoline compounds and on the enatioselectivity in hydrogenation was examined. Spectroscopic measurements in solution confirmed that oxazolines with one tripeptide or two monopeptide chains aggregate... More without a metal, while non-covalent intramolecular interactions are acting in all prepared metal complexes. The induction of chirality on the metal in the complexes was confirmed by CD spectroscopy; the crystal structures show that the metal atom is part of a helically chiral structure. The tendency to form aggregates of non-metal compounds and helical structures in metal compounds was analyzed by CREST/CENSO and DFT computational methods. Rh(I) and Ir(I) complexes of homo- and hetero-combinations of oxazoline bioconjugates and a literature-known triphenylphosphine with induction of chirality were used in the enantioselective hydrogenation of methyl-α-acetamidocinnamate, with obtained enantioselectivity up to 85%. Less

• Keywords: minokiseline; enantioselektivna hidrogenacija; helikalna kiralnost; nekovalentne interakcije; oksazolini; prijelazni metali; stereokemija
• Keywords (english): amino acids; enantioselective hydrogenation; helical chirality; non-covalent interactions; oxazolines; transition metals; stereochemistry
• Language: croatian
• URN:NBN: urn:nbn:hr:217:083448
• Promotion: 2025
• Project: Number: IP-2022-10-8456; Title: Supramolekulska asimetrična kataliza: Prijenos kiralnosti u koordinacijskim kavezima (Cage Cat); Title: Supramolecular asymmetric catalysis: Chirality transfer in coordination cages (Cage Cat); Acronym: Cage Cat; Leader: Srećko Kirin; Jurisdiction: Croatia; Funder: Hrvatska zaklada za znanost; Funding stream: Research Projects
• Project: Number: KK.01.1.1.04.0013; Title: Inovativna rješenja u katalitičkim proizvodnim procesima za potrebe farmaceutske industrije; Title: Innovative solutions in catalytic processes in the pharmaceutical industry; Acronym: CAT PHARMA; Leader: Srećko Kirin; Jurisdiction: eu; Funder: Europska unija; Funding stream: European Regional Development Fund
• Study programme: Title: Doctoral study; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica u području prirodnih znanosti (doktor/doktorica u području prirodnih znanosti)
• Type of resource: Text
• Extent: XLIII, 180 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2025-01-15 11:50:54