Studies on Organic Solid State for Design and Development of the Field of Fine Molecular Recognition

固体分子的精确识别与生物分子的精确识别有着密切的联系。固体分子识别的研究对于利用光学分辨和对映选择反应制备光学活性材料的新方法的发展也具有重要意义。利用主-客体络合物晶体进行了一些光学分辨和对映选择反应。在主客体复合物中，这两种组分相互识别分子的大小、形状和手性。通过对主-客体包合物的x射线晶体结构研究，探讨了分子识别的机理。根据分析结果，设计了几种新型主客体复合物。通过与具有光学活性的2,2′-二羟基- 1,1′-二萘基(1)络合，有效地溶解了一些硒和砷的氧化物。发现具有光学活性的9,9′-二羟基- 10,10′-联苯基(2)对一些be…More - ta-内酰胺衍生物的光学分辨是有效的。这些包合物的x射线晶体结构研究表明，1或2羟基与客体化合物之间的氢键形成是重要的。由酒石酸衍生的主体化合物(3)可用于氮化吡啶衍生物的光学分辨。虽然迄今为止肟的分离尚未成功，但一些环己酮肟通过与光学活性1,6 -二（邻氯苯）- 1,6 -二苯基六- 2,4 -二炔- 1,6 -二醇(4)络合有效地分离了。最有趣的分辨率是在固态中实现的。将旋光性宿主3和环氧化β -离子酮(5)在固态中混合得到旋光性3和旋光性5为88% ee的配合物。这表明在固体状态下发生了对映选择性络合。利用这一现象，还获得了一个有趣的5的动力学分辨率。我们发现许多有机反应在固体状态下高效而选择性地发生。在某些情况下，固体中的效率和选择性比溶液中的高得多。用Wittig-Horner试剂（如ph_3P=CHCOOEt）处理4-甲基或3,5 -二甲基环己酮- 3包合物，可得到58-73% ee的旋光性烯烃。在固体状态下，1∶2包合物4和环cta2,4,6 -三烯- 1 - 1(6)辐照得到光学活性的6光二聚体，而类似的1∶1包合物3和6辐照得到光学活性的分子内光环化产物。通过x射线晶体结构的研究，阐明了光反应的机理。通过改变宿主化合物来控制6的光反应类型和立体反应过程是有用的。醇缩反应在固态下也比在溶液中进行得快得多。当醛醇反应在具有旋光性主体的包合物中进行时，发生对映选择反应生成旋光性醛醇。少

Precise molecular recognition in the solid state are interesting in relating to that in living body. Studies of the solid state molecular recognition are also important in relating to development of new preparative method of optically active materials by optical resolution and enantioselective reactions. Some optical resolution and enantioselective reactions have been developed by using host-guest complex crystals. In the host-guest complex, the both components recognize the size, shape, and chirality of molecules each other. The mechanism of the molecular recognition has been studied by X-ray crystal structural study of the host-guest inclusion complex. By refering to the analyzed result, some new host-guest complexes were designed.1. By complexing with optically active 2, 2'-dihydroxy-1, 1'-binaphthyl (1), some selenoxides and arsine oxides were resolved efficiently. Optically active 9, 9'-dihydroxy-10, 10'-biphenanthryl (2) was found to be effective for optical resolution of some be … More ta-lactam derivatives. X-Ray crystal structural study of these inclusion complexes disclosed that hydrogen bond formation between the hydroxyl group of 1 or 2 and the guest compound is important. Host compounds (3) which were derived from tartaric acid are useful for optical resolution of aziridine derivatives. Although resolution of oxime has never been succeeded so far, some cyclohexanone oximes were efficiently resolved by complexation with optically active 1, 6-di (o-chlorophenyl) -1, 6-diphenylhexa-2, 4-diyne- 1, 6-diol (4). The most interesting resolution has been achieved in the solid state. Mixing the optically active host 3 and rasemic beta-ionone epoxide (5) in the solid state gave a complex of 3 and optically active 5 of 88% ee. This shows that an enantioselective complexation occurs in the solid state. By using this phenomenon, an interesting kinetic resolution of 5 has also been achieved.2. We found that many organic reactions occur efficiently and selectively in the solid state. In some cases, the efficiency and selectivity are much higher in the solid state than in solution. Treatment of inclusion complex of 4-methyl or 3, 5-dimethylcyclohexanone and 3 with Wittig-Horner reagent, for example, ph_3P=CHCOOEt in the solid state gave optically active olefin of 58-73% ee. Irradiation of a 1 : 2 inclusion complex of 4 and cycloocta02, 4, 6-trien-l-one (6) in the solid state gave optically active photodimer of 6, however, the similar irradiation of a 1 : 1 complex of 3 and 6 gave optically active intramolecular photocyclization product. X-Ray crystal structural study, clarified the mechanism of the photoreactions. It is useful to be able to control the type and steric course of photoreaction of 6 by changing the host compound. Aldol condensation reactions were also found to proceed in the solid state much faster than in solution. When the aldol reaction is carried out in an inclusion complex with optically active host, enantioselective reaction occurred to give optically active aldol. Less