D-block metal complexes with amino acid conjugates of oxazolines and triphenylphosphines as chiral catalysts in hydrogenation reactions

Bakija, Marija (2025) D-block metal complexes with amino acid conjugates of oxazolines and triphenylphosphines as chiral catalysts in hydrogenation reactions. Doctoral thesis, Institut Ruđer Bošković.

PDF - Published Version - other Download (8MB)

Abstract

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 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%.

Item Type:	Thesis (Doctoral thesis)
Uncontrolled Keywords:	amino acids; enantioselective hydrogenation; helical chirality; non-covalent interactions; oxazolines; transition metals; stereochemistry
Subjects:	NATURAL SCIENCES > Chemistry
Divisions:	Division of Materials Chemistry
Projects:	Project title Project leader Project code Project type Inovativna rješenja u katalitičkim proizvodnim procesima za potrebe farmaceutske industrije-CAT PHARMA Srećko Kirin KK.01.1.1.04.0013 EK Supramolekulska asimetrična kataliza: Prijenos kiralnosti u koordinacijskim kavezima (Cage Cat) Srećko Kirin IP-2022-10-8456 HrZZ
Depositing User:	Marija Bakija
Date Deposited:	15 Jan 2025 08:14
URI:	http://fulir.irb.hr/id/eprint/9444

Actions (login required)

View Item