The Design And Synthesis Of Novel Optically Active Cagelike Molecular Square

Recently, extensive attention has focused on cagelike aromatic molecules of optically active, on account of their unique structural features as well as potential applications in optics and electronics. Although great improvement has been achieved in synthesizing chiral aromatic molecules in foreign laboratories, to date, report on chiral aromatic molecules attained by template control is scant. Our work of synthesizing these unique molecules based on binaphthyl derivative provides the possibility of searching their potential value. In this dissertation, based on the preceding research of our laboratory, a new type of cagelike cyclophane, containing 1,1'-binaphthyl unit, the source of chirality and 1, 2-bis(4'-iodophenyl)acetylene connected by ethynyl was designed and synthesized successfully and their optical properties were preliminarily researched. Furthermore, synthesis of cyclophanes connected by 1,4-diiodobenzene and 4,4'-diiodobiphenyl was optimized and remarkably enhanced yields were obtained.In the second chapter, a rational route for synthesizing enantiopure 2,2'- diethynyl-1,1'-binaphthyl was contrived. From the enantiopure 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, an intermolecular oxidative coupling route was designed. And the crucial intermediate, 2-bis(4'-iodophenyl)acetylene was designed and synthesized. The synthetic route includes four general reactions. Monosilylethynyl derivative was obtained first, then exposure of the compound to three different linkers respectively under Sonogashira coupling condition, after removal of protecting group under mild condition, the diacetylene intermediates were obtained successfully. Then the diacetylenes were added to a solution of Cu(OAc)2 in pyridine by syringing to pseudo high dilution to minimize polymerization of the diacetylenes. Three desired cagelike molecular squares were obtained ultimately. The structures of the intermediates and target molecules were characterized by MS, IR, 1H NMR, 13C NMR, 13C DEPT NMR and the structures of target molecules were simulated in a computional method.In a word, in this dissertation, a new type of cagelike cyclophanes with novel, aesthetically pleasing and fascinating structure, in which three different linkers were connected to the 2- and 2'-positions of 1, 1'-binaphthalene template with ethynyl was designed and synthesized successfully.