Homogeneous hydrogenation of electron-deficient alkenes by using iridium-complexes

Semeniuchenko, Volodymyr

Homogeneous hydrogenation of electron-deficient alkenes by using iridium-complexes

Files

Semeniuchenko_Dissertation.pdf(3.12 MB)

Date

2009

Publication type

Dissertation

Abstract

It is shown and proven, that the flavonoids represent a unique class of alkenes, for which the homogeneous hydrogenation is not known till now (except for some functionalized representatives). It is proven, that assigned task could not be resolved via traditional (electrophilic) homogeneous hydrogenation. However, a new reaction was discovered, namely nucleophilic hydrogenation. At the current state the nucleophilic hydrogenation by Ir-complexes is only of academical significance. An investigation of the mechanism is needed for its practical usage. Homogeneous hydrogenation of 7-methoxy-3-(pyridin-2-yl)chromone is very effective both in its electrophilic and in nucleophilic versions, and affords the corresponding chroman-4-one in almost quantitative yield.

Summary in another language

Die Flavonoide stellen wie oben gezeigt eine einzigartige Klasse der Alkene dar, für die die homogene Hydrogenierung bis jetzt nicht bekannt war (außer bei einzelnen funktionalisierten Vertretern). Es wurde gezeigt, dass die gestellte Aufgabe über die traditionelle (elektrophile) homogene Hydrierung nicht gelöst werden kann. Es wurde jedoch eine neue Reaktion gefunden, die Nucleophilhydrierung. Nach dem jetzigen Stand der Entwicklung hat die Nucleophilhydrierung mit Ir-Komplexen nur akademische Bedeutung. Die Bestimmung des Mechanismus ist für praktische Nützung sehr wichtig. Die Homogenhydrierung von 7-Methoxy-3-(pyridin-2-yl)chromon ist sehr effektiv sowohl bei elektrophiler als auch in nukleophiler Durchführung, und liefert das entsprechende Chroman-4-on mit fast quantitativer Ausbeute.

Subject (DDC)

540 Chemistry

Keywords

homogen,Hydrierung,Reduktion,Iridium,Rhodium,Flavonoiden,Heterocyclen,Weichheit,DFT,Chiralität,homogeneous hydrogenation reduction,iridium,rhodium,flavonoids,heterocycles,computations softness,DFT,chirality,stereoselective

Cite This

ISO 690

SEMENIUCHENKO, Volodymyr, 2009. Homogeneous hydrogenation of electron-deficient alkenes by using iridium-complexes [Dissertation]. Konstanz: University of Konstanz

BibTex

@phdthesis{Semeniuchenko2009Homog-10023,
  year={2009},
  title={Homogeneous hydrogenation of electron-deficient alkenes by using iridium-complexes},
  author={Semeniuchenko, Volodymyr},
  address={Konstanz},
  school={Universität Konstanz}
}

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Examination date of dissertation

May 19, 2009