The Design And Synthesis Of Optically Active Three-dimensional Macrocycles

The chemistry of cyclophynes having carbon-carbon triple bond bridges has been one of the most actively investigated fields in modern cyclophane chemistry, particularly in connection with the evolving fields of carbon-rich materials and shapepersistent macrocyclic compounds.The properties of cyclophynes are characterized by the geometric and electronic properties of triple bonds and the substitution pattern of the aromatic rings.With regard to the geometrical properties,the macrocyclic frameworks of cyclophynes can be expanded by incorporation of triple bonds because of their linearity.The substitution pattern of the aromatic rings,on the other hand,fixes the direction of the bridging triple bonds,defining the whole molecular shape.As a result,a variety of two-and three-dimensional architectures can be built by connecting aromatic rings with triple bond linkages.On the other hand,nonplanar macrocycles of this type have been studied with regard to their conformation,chirality,and their potential application to liquid crystalline and sensing materials.Some highly unsaturated members of this type of compound have been shown to serve as precursors of ordered carbon materials.On the base of our labe was described,and a series of new type of cyclophynes and their derivatives were designed and synthesized.Because of the stability of binaphthalene's configuration in the reactions and the fine directional function of ethynyl in the space,enantiopure 2,2'-diethynyl-1,1'-binaphthyl was used as synthetic template for the synthesis of target molecules.In the second chapter in this paper,the synthesis of enantiopure[(R)-or(S)-form] 2,2'-diethynyl-1,1'-binaphthyl was described.2,2'-Diethynyl-1,1'-binaphthyl was synthesized from binapythol by esterification of hydroxyl,Kumada reaction of sulfonic ester with Grignard reagent,bromination of methyl,hydrolyzation of dibromomethyl and especial Wittig reaction.In the third chapter,three-dimensional cage-like cyclophanes 76 were designed and synthesized from enantiopure[(R)-or(S)-form]2,2'-diethynyl(dihydroxy)-1, 1'-binaphthyl,However we have not been given to benzene for the plane of target compounds and got a strange three-dimensional,cage-like cyclophanes.And in the process of synthetic routes involved reaction of several types:Sonogashira reaction, Sealed-tube reaction and Eglinton coupling reaction. In the forth chapter,we solved the problem of steric hindrance in the third chapter. Through the CPK model of the Chem3D molecular modeling and simulation,we design a three-dimensional compound 91 with an extension trigeminal benzene-acetylene as a flat connecting bridge,three-dimensional cage-like cyclophanes 94 were designed and synthesized though Eglinton coupling reaction from enantiopure[(R)-or(S)-form]2,2'-diethynyl(dihydroxy)-1,1'-binaphthyl.All the intermediates and target compounds synthesized in this paper were characterized by MS,IR,¹H NMR,¹³C NMR and DEPT...