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Synthesis of C2 Chiral Bidentate Diamine Ligands Derived from Macrocyclic Troger Base and Its Application to Asymmetric Synthesis

大环Troger碱衍生的C2手性二齿二胺配体的合成及其在不对称合成中的应用

基本信息

批准号：
11640539
负责人：
MIYAHARA Yuji
金额：
$ 2.24万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

We have succeeded in developing an efficient synthesis of a macrocyclic Troger base with a polyether tether (Trogarophane) by reacting triethylene glycol bis (p-aminophenyl) ether and formalin in HCl-EtOH solution at 80℃ for 18 h. Since the molecular cavity found to be too small for use as a cyclophane host, we turned to the outer dinitrogen moiety. It was expected that when the endo-methylene group is removed, the resulting diamine will become a promising bidentate ligand and, because the inversion is prohibited by the polyether tether, the C2 chiral properties of Troger base will be preserved. Removal of the endo-methylene bridge was not straightforward, because the ether oxygen made the already electron-rich benzene ring more reactive towards oxidixing agents. On successive treatments with trifluoroacetic anhydride and methanolic sodium carbonate the diNH compound was obtained. Methylation of one or both of the nitrogen atoms was completely controlled by suitable selection of the reaction conditions. The optical resolution of all the compounds was effectively accomplished by use of a chiral column (Chiralcel OJ) with increasing efficiency diNMe<NHNMe<Tr o gerophane<diNH.Although the separation for the diNH compound was really remarkable, for the reasons of wide applicability Tr o gerophane was mainly separated. It is gratifying that rather sparingly soluble racemic Trogerophane becomes very soluble on separation so that considerable amounts can be applied on the column with the use of cosolvent. Determination of the absolute structure of the separated Trogerophane is underway.Since the metal ion complexation was confirmed with several kinds of elements, we are currently examining the right conditions for asymmetric synthesis.

通过三甘醇双(对氨基苯基)醚和福尔马林在80℃的盐酸-乙醇溶液中反应18h，我们成功地合成了大环Troger碱与聚醚醚(Trogarophane)，由于分子腔太小而不能用作环番的宿主，我们转向了外氮部分。预计当内亚甲基被移除时，生成的二胺将成为一种很有前途的双齿配体，并且由于聚醚链条阻止了转化，因此Troger碱的C2手性将被保留。去除亚甲基内桥并不是一帆风顺的，因为乙醚氧使已经富含电子的苯环对氧化剂更具活性。再用三氟乙酸酐和甲醇碳酸钠处理，得到丁二烯化合物。通过选择合适的反应条件，可以完全控制一个或两个氮原子的甲基化。利用手性色谱柱(Chiralcel OJ)有效地实现了所有化合物的光学拆分，提高了拆分效率。虽然对Dinh化合物的拆分效果很好，但由于适用范围广，Tr o Gerophane主要是拆分。令人欣慰的是，相当少溶解的外消旋Trogerophane在分离时变得非常易溶，因此可以使用助溶剂将相当数量的色谱柱应用于柱上。分离的Trogerophane的绝对结构正在确定中，由于金属离子与几种元素的络合被证实，我们目前正在研究不对称合成的合适条件。