The Design And Synthesis Of Specific Structure Cyclophynes With Template

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. The previous work of our lab was described, and a series of new type of cyclophynes and their derivatives were designed and synthesized.The second chapter focused on the synthetic method of the helical cyclophane. (R) and (S)-2,2′-diethynyl-1,1′-binaphthyl with highly stable chiral configuration was employed as structural template, an unsymmetrical helical cyclophane (R,P)-67 bridged by different components was successfully achieved by the method reported in the literature. The enantiomer (S,M)-67 was successfully achieved by a new synthetic strategy. In comparison with the previously reported method, improved new one saved the preparation of some chiral building block, and shorted synthetic processes. The design and synthesis of enantiopure compounds with cage structure were described. Enantiopure molecule square (R,R,R,R) and (S,S,S,S)-69, 70 were synthesized from the same chiral templates. The Ag(I) complex of (R,R,R,R) and (S,S,S,S)-69 and Cu(II) complex of (R,R,R,R) and (S,S,S,S)-70 was obtained quantitatively. A dramatic change of 1H NMR and circular dichroism (CD) spectra was observed compared to 69, 70. But also the CPK model and the calculated result of Chem3D, given the complex structure of the double helix molecule compounds. Their CD spectra represented exactly mirror images of each other, which reflected unambiguously enantiomeric relation between the all isomers.In the third chapter, several enantiopure Dumbbell-compounds [(R,P),(R,P)]-79~82 and dentritic compound [(R,P),(R,P),(R,P)]-83~86 with helical units were synthesized from (R)-2,2′-dihydroxy-1,1′-binaphthyl(BINOL) by Sonogashira coupling reaction. In the structures of these compounds, cyclophyne bearing helical structure and rigid phenylethynyl were used as the ball of dumbbell and linking bridge. And their space models were given using Chem3D. The molecular sizes of compounds 79-86 are 2-3 nm, which makes these compounds have potential application as nanomaterials.In the fourth chapter, (R,R) and (S,S)-72 with double helical structure bridged by o-phenylene were designed and synthesized from enantiopure [(R)-or(S)-form] 2,2'-diethynyl(dihydroxy)-1,1'-binaphthyl. The first method, we attempt obtained the torgetmolecular by intermecular coupling reaction, but obtained a monomer of intramolecularly coupling cyclization 154,159. Subsequently, we synthesis of 72,74 was successfully achieved by a new synthetic strategy. by the introduction of protecting group and the conneting of a o,o′-butadiyne linking bridges, then removal of protecting group, leading-in another o′-phenylene linking bridges and intramolecular Eglinton coupling reaction. 154 and 73 were characterized by X-ray single crystal diffraction.In the fifth chapter, we designed two three-dimensional macrocycles 89 and 90 with different sizes of the cavity. But 89 can not be synthesized by the two synthetic strategy we designed, because of the molecular steric effect. By extended the linking bridges, through Sonogashira reaction, sealed-tube reaction and Eglinton coupling reaction. Obtained the three-dimensional macrocycles 90.All the intermediates and target compounds synthesized in this paper were characterized by MS, IR, 1H NMR, 13C NMR and DEPT.