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

固体中的精确分子识别与活体中的分子识别是有趣的。固体分子识别的研究对于发展光学拆分和对映体选择性反应制备光学活性材料的新方法也具有重要意义。利用主客体络合物晶体进行了一些光学拆分和对映体选择性反应。在主客体复合体中，这两个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，设计了一些新的主客复合体。通过与旋光性的2，2‘-二羟基-1，1’-联萘(1)络合，有效地拆分了一些硒和砷氧化物。光学活性的9，9‘-二羟基-10，10’-联苯基(2)对某些Be-…的光学拆分是有效的更多的乙内酰胺衍生品。这些包合物的X射线晶体结构研究表明，1或2的羟基与客体化合物之间形成氢键是重要的。酒石酸衍生的主体化合物(3)可用于氮杂环丙烷衍生物的光学拆分。尽管迄今拆分一直没有成功，但通过与光学活性的1，6-二(邻氯苯基)-1，6-二苯基-2，4-二炔-1，6-二醇(4)络合，一些环己酮肟被有效地拆分。最有趣的分辨率是在固态下实现的。将光学活性主体3和旋光性β-紫罗兰酮环氧化物(5)在固态中混合，得到了3和光学活性5的络合物，其ee为88%。这表明在固体状态下发生了对映体选择性络合反应。通过利用这一现象，还获得了有趣的动力学分辨率5。我们发现许多有机反应都是在固体状态下高效和选择性地发生的。在某些情况下，固态的效率和选择性远高于溶液。用Wittig-Horner试剂处理4-甲基或3，5-二甲基环己酮与3的包合物，如ph3P=CHCOOEt，得到光学活性烯烃58-73%ee。4和环辛二烯-L-酮(6)的1：2包合物在固体中照射得到光学活性的光二聚体6，而3和6的1：1包合物在固体中照射得到光学活性的分子内光环化产物。X-射线晶体结构研究，阐明了光反应机理。通过改变主体化合物来控制6的光反应类型和空间过程是有用的。研究还发现，羟醛缩合反应在固态比在溶液中进行得快得多。当Aldol反应在具有光学活性主体的包合物中进行时，发生不对称反应得到光学活性Aldol。较少

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