Bronsted Acid Catalyzed Aza-Baylis-Hillman Reaction

In this thesis, firstly we viewed the development of aza-Bayllis-Hillman reaction in recent years, then, the aza-Bayllis-Hillman reactions catalyzed by achiral phosphite and chiral phosphoric acid with steric hindrance at 3,3'-position were studied, and the target compoundsα-methylene-β-aminocarbonyl derivatives in the form of racemates and chiral materials were obtained:1. The aza-Bayllis-Hillman reactions of imines and methyl acrylate catalyzed by achiral phosphite were studied. The reaction conditions, such as solvent, temperature, concentration, catalysts, and substrates were screened. The target aza-Bayllis-Hillman reaction products were obtained with 25-79% yield, which provided the racemates for the chiral phosphoric acid catalyzed aza-Bayllis-Hillman reactions.2. A series of chiral phosphoric acid with steric hindrance at 3,3'-position were synthesized via multistep transformations from cheap and readily available (R)-BINOL, including pretection of hydroxyl group, Suzuki or Kumada coupling reaction, depretection, reaction with POCl3 under alkaline condition, then hydrolysis. And these chiral phosphoric acids were characterized by 1H-NMR,13C-NMR, MS and [α]D20, respectively. 3. Subsequently, we applied these chiral phosphoric acids to the asymmetric aza-Bayllis-Hillman reactions of imines and methyl acrylate. And different solvents, br(?)nsted acids, substrates were investigated. As a result, the reaction with the solvent of 1,4-dioxane, catalyzed by catalysis 18 was finished with 80% yield and 31% enantioselectivity.