Development of Chiral Cyclophanes for Molecular Recognition and Their Application

本项目的目的是制备由两个手性1，1 '-联二萘酚部分和两个芳香桥组成的光学活性环番，以研究分子内相互作用和通过旋光的变化可逆记录光信息。1.合成了多种光学活性的环蕃化合物（1）：在碳酸钾存在下，手性1，1 ′-联萘（2）（2 mol当量）与二卤代物（3）在丙酮中反应，以高产率得到半桥连中间体（4）。当2和4（摩尔比1：1）缓慢加入到碳酸钾的丙酮悬浮液或氢化钠的DMF悬浮液中时，环蕃（1）的产率较高（40-70%）。以对，对′-二溴甲基二苯甲酮为2，得到含羰基的1，并由此合成了含两个1.2单元的手性双环芳（4）。1与各种分子（客体）的分子间相互作用可以通过旋光度的变化来研究：与客体的相互作用改变了1的构象，从而引起旋光度的变化。我们发现1与客体络合的平衡常数可以通过旋光度的变化来估算.利用含偶氮基团的手性环蕃可逆记录光信息：紫外光照射使反式偶氮基团异构化为顺式偶氮基团。这种现象可以通过旋光度的变化来检测。加热将顺式几何结构转化为反式几何结构，以使旋光度返回到起始点。

The purpose of this project is to prepare optically active cyclophanes, which are composed of two chiral 1,1'-binaphthol moieties and two aromatic bridges, in order to investigate intramolecular interaction and reversible record of light information by the change of optical rotation.1. Many kinds of optically active cyclophanes (1) were synthesized : In the reaction of chiral 1,1'-binaphthol (2) (2 mol equiv) with dihalide (3) in the presence of potassium carbonate in acetone, and semi-bridged intermediate (4) was obtained in an excellent yield. When 2 and 4 (1 : 1 mol ratio) were slowly added to a suspesion of either potassium carbonate in acetone or sodium hydride in DMF, the expected cyclophane (1) was given in a good yield (40-70%). Use of p, p'-bis(bromomethyl)benzophenone as 2 afforded a carbonyl-contained 1, from which we synthesized a chiral double-cyclophane (4) having two units of 1.2. Intermolecular interaction of 1 with various molecules (guests) can be investigated by the change of optical rotation : Interaction with the guest changes the conformation of 1 to cause the change of optical rotation. We showed that the equilibrium constant for complexation of 1 and the guest can be evaluated by the change of optical rotation.3. The chiral cyclophane having azo group is utilized for reversible record of light information : Ultraviolet irradiation isomerizes trans azo group to cis one. This phenomenon can be detected by the change of optical rotation. Heating converted the cis geometry to trans one to return the optical rotation back to the starting point.