Asymmetric Michael Addition And Tandem Reaction Catalyzed By Chiral Primary-Secondary Diamines

This dissertation mainly focused on the synthesis of newly designed chiral primary-secondary diamine catalysts and their applications in asymmetric Michael addition and tandem reactions.In the first part, the newly-designed chiral primary-secondary diamine catalysts were synthesized from natural amino acids, and proved to be good catalysts for the asymmetric Michael addition of malonates to a,β-unsaturated enones. Under the optimized conditions, the reaction can afford the products in high yields (up to 99%) and enantioselectivities (up to>99% ee). Based on these results, a stereochemical model has been developed to account for the selectivities.In the second part, several catalysts with bulky group in the secondary amine moiety were synthesized, and applied in the asymmetric Michael addition of nitroalkanes to a,P-unsaturated enones. Under the optimized conditions, by employing catalyst C12, up to 99% yield and 92% enantioselectivity were achieved for chiral products with nitro group.In the third part, tandem Michael-Aldol-Dehydration reactions were exploited by using simple chiral primary-secondary diamine catalyst. Under the optimized conditions, the reaction can afford the chiral polyfunctional cyclohexenones in high yields (up to 98%) and enantioselectivities (up to>99% ee). Thus, the present method may be one of the most convenient ways to this kind of chiral moleculeIn the last part, we achieved the asymmetric alkynylation of trifluoromethyl ketones using Et2Zn and ligand E49 derived from camphor. Under the optimized conditions, the reaction can afford the chiral fluorinated molecules in good yields and moderate enantioselectivities.