Bifunctional organocatalysis in the asymmetric Aza-Baylis-Hillman reaction

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