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Philipps-Universität Marburg
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Over the past decade, chiral iron catalysts have attracted much attention due to their low toxicity and abundance on earth. Therefore, the design of ligand, configuration stability, and application of catalysts are important research topics. This thesis mainly deals with synthesizing new chiral-at-iron complexes and the enantioselective C-H amination with chiral N4 iron catalysts.
Chapter 2.1 New octahedral chiral-at-metal iron(II) complexes with modified ligands were synthesized to expand the family of previous complexes in our group. The new design of ligands could be divided into two types, one are the cis-coordinated N-(2-pyrimidyl)-substituted imidazolylidene bidentate ligands, and the other are the cis-coordinated N-(4,5-pinene)-substituted imidazolylidene bidentate ligands. In addition, the central metal iron(II) is coordinated with two monodentate acetonitriles, and two hexafluorophosphate ions supplement the octahedral coordination sphere. These chiral-at-iron complexes were constitutionally stable and enantiomeric enriched as confirmed by 1H NMR and CD spectroscopy. In asymmetric catalytic reactions, the configuration stability of the new chiral-at-iron catalysts remained an open question.
Chapter 2.2 Asymmetric secondary C-H bonds amination reactions with a series of chiral N4 iron catalysts are demonstrated, forming cyclic urea products with a broad scope for 34 examples with up to 99% yield and 95% ee, including benzylic, allylic, propargylic, and completely non-activated aliphatic C(sp3)-H bonds.
Chapter 2.3 A simple and efficient enantioselective synthesis method based on enantioconvergent nitrene C(sp3)-H insertion was developed. The racemic disubstituted N-benzoyloxyurea substrates catalyzed by chiral a N4 iron catalyst obtained more than 30 examples, with up to 99% yield and up to 90% ee.
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Created: 2022Issued: 2025-11-26Updated: 2022-11-08
Faculty
Fachbereich Chemie
Language
ger
Data types
DoctoralThesis
Keywords
der enantioselektiven C-H-Aminierung mit chiralen N4-Eisen-Katalysatoren;das Design der Ligandenthe design of ligandconfiguration stability, and application of catalystsdie Konfigurationsstabilität und die Anwendung der Kenantioselective C-H amination with chiral N4 iron catalysts
DFG-subjects
chirale Eisenkatalysatorenasymmetrischer Reaktionchiral-at-iron Komplexe
DDC-Numbers
540
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Cui, Tianjiao: Design chiraler Eisenkomplexe zur Katalyse asymmetrischer Reaktionen. : Philipps-Universität Marburg 2025-11-26. DOI: https://doi.org/10.17192/z2023.0048.