Bifunctional organocatalysis in the asymmetric Aza-Baylis-Hillman reaction
type: CreativeWork
description: In this doctoral thesis, the mechanism of the Lewis base-mediated aza-Baylis-Hillman reaction was examined. Intermediates of the reaction were intercepted and structurally characterized, an extensive kinetic study was performed and the effects of Brønsted acidic co-catalysts on the reaction mechanism were examined. In addition, other mechanistic aspects like reversibility, stability of the stereocenter and chirality transfer from the catalytic system to the reaction product were studied. This mechanistic study provided useful information for the rational design of an appropriate chiral catalytic system. Several potential catalytic systems were synthesized and tested. The most successful system involved a reaction medium, an ionic liquid, as the source of chirality. With this system, enantioselectivities up to 84% ee were obtained in the triphenylphosphine-catalyzed aza-Baylis-Hillman reaction of aromatic tosylaldimines and methylvinyl ketone.
abstract: In this doctoral thesis, the mechanism of the Lewis base-mediated aza-Baylis-Hillman reaction was examined. Intermediates of the reaction were intercepted and structurally characterized, an extensive kinetic study was performed and the effects of Brønsted acidic co-catalysts on the reaction mechanism were examined. In addition, other mechanistic aspects like reversibility, stability of the stereocenter and chirality transfer from the catalytic system to the reaction product were studied. This mechanistic study provided useful information for the rational design of an appropriate chiral catalytic system. Several potential catalytic systems were synthesized and tested. The most successful system involved a reaction medium, an ionic liquid, as the source of chirality. With this system, enantioselectivities up to 84% ee were obtained in the triphenylphosphine-catalyzed aza-Baylis-Hillman reaction of aromatic tosylaldimines and methylvinyl ketone.
author: Buskens, Pascal
language: eng
keywords: info:eu-repo/classification/ddc/660, Technische Chemie, Organokatalyse, Reaktionsmechanismus, Asymmetrische Synthese, Chirale Lösungsmittel, Ionische Flüssigkeiten, organocatalysis, reaction mechanism, asymmetric synthesis, chiral solvents, ionic liquids
date published: 2006
date modified: 2026-07-30T19:43:10Z
provider: RWTH Aachen University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: Publikationsserver der RWTH Aachen University