【作者】 陈强；

【导师】 安德烈；

【作者基本信息】 湖南大学 ， 有机化学， 2009， 博士

【摘要】 以碳-碳三键为桥联的环芳化学,特别是富碳化合物和构型保持的大环类化合物研究。是现代环芳化学研究中最引人注目的领域。环芳化合物的性质取决于它的几何形状、电子效应和芳环上的取代基。三键的刚性结构可以使大环骨架得以很好的扩展,而苯环可以控制三键桥联的方向,从某种意义上决定了整个分子的形状。三键和芳香环的组合可以形成一系列形态各异的平面或三维环芳化合物。通过C≡C的连接,各种芳香环可以组合成形状特定的二维或三维的大环化合物。它们在分子构型、分子手性、液晶材料和传感材料等方面的潜在应用被广泛研究。其中一些高度不饱和的此类化合物被作为是有序碳材料的前驱体。本文还进一步阐述了本实验室以前的工作,在此基础上设计并合成了一系列新型的光学活性的环芳化合物及其衍生物。第二章主要讨论光学活性分子内双螺旋化合物的构筑方法。通过手性构型高度稳定的联萘模板来引进手性源,用文献报道的此类双螺旋化合物合成方法合成了具有两个不同连接桥的分子内双螺旋化合物(R,P)-67,并设计了新的合成路线合成了该双螺旋化合物的对映异构体(S,M)-67,通过比较得出新方法省去了一些复杂手性片段的制备,缩短了反应步骤。从(R)和(S)-2,2’-二乙炔基-1,1’-联萘模板出发,还成功地合成了光学活性分子方(R,R,R,R)-和(S,S,S,S)-69和70,我们将化合物69和70分别与六氟磷酸银和六氟磷酸铜以等摩尔比混合。虽然未得到可以进行X-Ray分析的化合物晶体,但对形成的配合物进行了1HNMR和圆二色谱(CD)分析。通过与69和70的比较,我们发现1HNMR的氢位移值和圆二色谱(CD)的Cotton效应波长、峰形都有很大的变化。我们可以判定金属配合物的形成,由于这两个笼状化合物含有氮朝向环内的吡啶和联吡啶单元,只能与金属离子形成分子内配合物。而且通过CPK模型和Chem3D的计算,给出了配合物的结构为分子内双螺旋化合物。这表明我们通过含有吡啶单元的笼状化合物与金属配位构筑了一种新型的分子内双螺旋化合物,且异构体的CD谱呈现出良好的镜像对称关系,这表明了异构体为对映异构体。第三章从(R)和(S)-2,2’-羟基-1,1’-联萘出发,以具有双螺旋结构的环芳化合物为哑铃的球体,刚性的苯基炔化合物为连接桥,通过Sonogashira偶联反应成功地合成了几个光学活性的哑铃状化合物(R, P)-和(S, M)-79~82以及螺旋单元构筑的枝状化合物(R, P)-和(S, M)-83~86。目标化合物的结构都通过IR,1H和13C NMR分析得到确认,而且对其进行了紫外–可见吸收光谱和圆二色谱分析。并且通过Chem3D的计算得出,目标化合物的分子大小都达到了2-3个纳米,从而可以展望此类分子在纳米材料方面的应用。第四章以(R)和(S)-2,2’-二乙炔基(羟基)-1,1’-联萘以及为模板,引入邻位苯环连接桥构筑的两个扩展型双螺旋化合物。并从两个模板出发,在最初尝试由分子间成环合成目标化合物时,却得到了目标化合物的单倍体(分子内成环化合物)。在此基础上改进了合成策略,设计了对模板进行选择性保护,先引入一边二炔连接桥,再脱去保护引入另一端邻位苯环连接桥,最后经Cu2+催化的分子内Eglinton偶合成环反应得到了设计的目标化合物。并成功得到了化合物154,73的适合X-Ray单晶衍射分析的晶体,对其进行了晶体结构分析。第五章设计了两个空穴大小不同的三维空腔结构分子89和90。在89的合成中,虽然设计了分子内和分子间关环两条合成路线,但由于分子位阻效应未得到设计的目标分子,却都得到了一个双层笼状化合物175。目标化合物90引入了更长的苯炔体系作为平面连接桥,减小了联萘间的位阻,直接由分子间成环合成法得到。在此过程中我们还探讨了合成路线中涉及的几种反应类型:Sonogashira反应,脱去保护基TMS的反应,封管反应,铜盐促进的炔烃偶合反应。本文当中所有的中间体和目标化合物都经过MS、IR、1H NMR、13C NMR和DEPT组合测定得到确认。更多还原

【Abstract】 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.更多还原