Template Synthesis Of Optically Active Cagelike Cyclophanes

Optically active cyclophanes, such as helical molecules and three-dimensional, cagelike cyclophanes have been the subject of extensive investigation from the standpoints of structural chemistry and material science. The fundamental sources of the interest in cyclophanes include the conception of novel, aesthetically pleasing and interesting structures, the challenge of synthesizing them, and the study of their properties once they had been prepared. Their unique structural features (Ï€-conjugated, helicity) indicate their potential applications in optics and electronics. In this thesis, based on the preceding research of our laboratory, a new type of cagelike cyclophanes, in which 1,1 '-binaphthyl unit ,the source of chirality and three different linkers(2,6-dibromopyridine, 1,4-diiodobenzene, 4,4'-diiodobiphenyl) connected by ethynyl was designed and synthesized successfully and their optical properties were preliminarily researched.In the second chapter, a rational synthetic route for enantiopure 2,2'-diethynyl-1,1 '-binaphthyl was established. From the optically active 2, 2'-dihydroxy-1,1 '-binaphthyl, through esterification, Kumada coupling, bromization, hydrolization and Wittig elimination reaction, 2,2'-diethynyl-1,1'-binaphthyl was obtained.In the third chapter, in order to synthesize the target molecules, a intermolecular oxidative coupling route was designed . Some important intermediates should be obtained to fit the topological demand of the target molecules. The synthetic route includes four general reactions. Monosilylethynyl derivative was obtained first, then exposure of this compound to three different linkers separately under Sonogashira reaction condiction, after removal of protective group under mild condition, the diacetylene intermediates were obtained successfully. The diacetylenes were then added to a solution of Cu(0Ac)2 in pyridine by syringe pump to achieve pseudo high dilution conditions to minimize polymerization of the starting material. Then three kinds of cagelike target molecules were obtained finally. The structures of the new intermediates and target molecules were identified by IR, ¹H NMR, ¹³C NMR, ¹³C DEPT NMR and the structures of target molecules were simulated in a computational chemistry way.