The Synthesis Of Multifunctional Multiple Hydrogen Bonds' Guanidine-amide Catalysts And Their Applications In Asymmetric Multi-component Reactions

Guanidine-amide catalysts play a catalytic role through hydrogen bonding and activation of electrophilic reagents.The guanidine-amide catalysts,which based on BINOL framework,contain chiral alkaloids,bridged tert-nitrogen bases and guanidine hydrogen bonds.Through three parts of synergistic action,guanidine-amide catalysts play a role of high catalytic activity and high stereoselectivity.My research contents are described from the following two aspects:With the 3-hydroxy-2-naphthoic acid in the market as ingredients,C₂-axis chiral structure of binaphtholic acid framework can be synthetized through four-steps which contain esterification,coupling,demethylation and resolution.Then introducing guanidine into binaphthalene skeleton by DCC-HOBt condensation,a kind of chiral guanidine-amide catalysts with hydroxyl,acyl and guanidine groups are synthesized.The chiral guanidine-amide catalysts are used to catalyze mult-icomponent reactions of the Biginelli reaction of 3,4-dihydropyrimidine and the synthesis of 1,4-dihydropyridine compounds.And the catalytic and reaction conditions of the catalyst are optimized.The optimum reaction conditions for Biginelli reaction are as follows:at the 50?,2 mL ethyl acetate as solvent,10 mmol%catalyst for 24 h,eleven 3,4-dihydropyri-midinone compounds with optically active were obtained.The highest yields and enantioselectivity are up to 90%and 78%.The optimum reaction conditions for the synthesis of 1,4-dihydropyridine compounds are as follows:at 50?,2mL toluene as solvent,15 mmol%catalyst for 48 h,twelve kinds of 1,4-dihydropyridine compounds with optical activity are obtained.The highest yields and enantioselectivity are up to 65%and 60%.The structures of all compounds were characterized by ¹H NMR,¹³C NMR,IR and melting point.