The Asymmetric Knoevenagel Condensation Catalyzed By Chiral Tertiary Amines

Knoevenagel condensation is a common and powerful synthetic method for forming carbon-carbon bonds in organic synthesis, which is also the typical modern organic reaction, Regardless of its long history of research and industrial applications,the research on asymmetric catalytic Knoevenagel reaction is seldom reported. This thesis mainly report a variety of small molecules chiral tertiary amine catalysts from(S,S)-hexamethylene diamines. And particularly studied about its applications in asymmetric Knoevenagel condensation reaction as follows:Primarily, we reported a simple route to prepare chiral tertiary amine catalyst,(S,S)-hexamethylene diamine as raw material, through acylation, carbonyl reduction, N-alkylation reaction to synthesize 4 chiral cyclohexane diamines derived tertiary amine with high yield. The structures of the products were confirmed by 1H-NMR and MS.Secondly, we studied the synthesis of 2-phenylpropionaldehyde derivatives--the substrates of asymmetric Knoevenagel condensation, through the Darzens condensation or Corey-Chaykovsky epoxidation reaction of two different synthetic routes, we prapared 12 2-phenylpropionaldehyde derivatives. By single factor experiment, the optimum reaction conditions were determined, and the product structure detected by 1H-NMR.Finally, we used the chiral tertiary amine catalysts in asymmetric Knoevenagel condensation reaction, with the reaction of 2-phenylpropionaldehyde and diethylmalonate as a model, through the single factor experiment of catalyst, solvent, reaction temperature to determine the optimal reaction conditions are studied. And under this conditions to the Knoevenagel condensation 5 different desired products were obtained. The products were determined by 1H-NMR, 13C-NMR an chiral HPLC.