Reactions and Structures of Crystalline Molecular Assembly

在晶体分子组合中，如晶体主客体包合物，分子有规律地排列，化学反应有选择性地进行。当使用手性宿主时，前手性客体分子以手性形式排列在包合物中。包合物中的前手性客体进行光化学或热化学反应可得到手性反应产物。另一方面，当宿主与同分异构体的混合物选择性地发生包合作用时，可以通过包合作用进行同分异构体的分离。当使用手性宿主时，可以实现对映体的分离。此外，在这些晶体分子组装中，分子异构如互变异构被限制或冻结，然后一个互变异构可以以纯形式分离出来。在这些课题中，我们的协作工作已经完成。1)非手性氧酰胺与酒石酸衍生的手性宿主化合物形成包合物。包合晶体在固体状态下的光照射得到光学活性的β -内酰胺衍生物。在大多数情况下，固体反应的对映选择性很高。用x射线晶体结构分析研究了前手性氧酰胺分子的手性排列。另外一些具有二烯基团的前手性化合物也以手性形式排列在具有手性主体的包合晶体中，晶体的光照射产生具有光学活性的2+2光环化产物。2)酒石酸衍生的2-环己酮包合物和手性宿主与固态亲二酚反应，得到具有光学活性的Michael加成产物。在固相反应中，亲二酚能识别2-环己酮分子平面的上、下两个方向。3)研究了部分含酚类衍生物的铵盐主体化合物的x射线晶体结构。

In crystalline molecular assemblysuch as crystalline host-guest inclusion complex, molecules are arraged regularly and then chemical reactions would proceed selectively. When chiral host is used, prochiral guest molecules are arranged in a chiral form in the inclusion complex. Photochemical or thermochemical reactions of the prochiral guest in the inclusion complex would give chiral reaction product. On the other hand, when the inclusion complexation between host and a mixture of isomers occurs selectively, separation of isomers can be carried out by the inclusion complexation. When a chiral host is used, separation of enantiomers can be accomplished. Furthermore, in these crystalline molcular assembly, molecular isomerization such as tautomerism is restricted or frozen, and then one tautomer can be isolated in pure form. In these topics, our collaboration works have been done.1) Achiral oxoamides formed inclusion complex with chiral host compound derived from tartaric acid. Photoirradiation of the inclusion crystal in the solid state gave optically active beta-lactam derivative. In most cases, enantioselectivity of the solid state reaction is very high. Arrangement of the prochiral oxoamide molecules in a chiral form has been studied by X-ray crystal structure analysis. Some other prochiral compounds which have diene grooups are also arrranged in a chiral form in an inclusion crystal with chiral host, and photoirradiation of the crystal gave optically active 2+2 photocyclization product.2) Reaction of an inclusion complex of 2-cyclohexenone and a chiral host derived from tartaric acid with dienophile in the solid state gave optically active Michael addition product. In the solid state reaction, dienophile recognizes the upside and downside of the molecular plane of 2-cyclohexenone.3) Some ammonium salt host compounds included phenole derivatives X-ray crystal structures were studied.