Selfassembly of Molecules in Crystal and Its Application to Selective Synthesis

将主客体包裹体晶体中的手性识别应用于客体化合物的光学拆分是成功的。从酒石酸衍生的光学活性主体化合物被发现对各种客体化合物的光学拆分是有效的。光学活性的双乙烯醇主体化合物对手性的识别依赖于其化学结构。例如，尽管光学活性的双乙烯醇主体对前列腺素合成的重要起始原料羟基环戊酮的拆分效果不好，但具有对二取代苯基的双乙烯醇主体化合物对拆分效果很好，但马钱子碱等生物碱对苯甲醇衍生物的拆分效果很好。有趣的是，一个苯基的间位或对位上有取代基的苯甲醇通过与Bru…的络合被有效地拆分更多的电影。而具有邻位取代基的苯并氢则不是。手性识别中的结构依赖性似乎与有机化学中所谓的溶液中的邻位效应有关。最有趣的发现是与辛可尼定主体的手性识别。N-苯甲酰辛可尼与2，2‘-二羟基-1，1’-联萘形成1：1包结晶体。通过络合作用，后者得到了非常有效的拆分。X-射线晶体结构分析表明，联萘酚的羟基与氯离子形成了氢键网络。有趣的是，N-苄基辛可尼二氯对10，10‘-二羟基-9，9’-联苯二酚不起作用，而10，10‘-二羟基-9，9’-联苯很容易被N-丁基辛可尼氯化物络合分解。在包合物晶体中的对映选择性反应研究中取得了一些成果。例如，环己酮和香豆素在其包合物晶体中与光学活性主体化合物进行光照射得到光学活性二聚体。用光学活性主体与丙烯酰胺包结物晶体进行光照射，得到了光学活性的二氢喹啉酮衍生物。这些光反应在包合物晶体中的对映体选择性几乎是完美的，得到了光学上几乎是纯的对映体。包合物晶体中的不对称Michael反应也是成功的，也揭示了大多数手性主体作为手性移位试剂。较少

Application of the chiral recognition in a host-quest inclusion crystal to optical resolution of the guest compound is successful. The optically active host compounds which were derived from tartaric acid were found to be effective for optical resolution of various guest compounds. Chiral recognition by the optically active diacetylenic alcohol host compound depends delicatelly on its chemical structure. For example, although the optically active diacetylenic alcohol host is not effective for the resolution of an important starting material of prostaglandin synthesis, hydroxycyclopentenone, the diacetylenic alcohol host compound which has p-disubstituted phenyl group between the two acetylenic groups works very well for the resolution.However, alkaloid such as brucine was found to be effective for the resolution of benzhydrol derivatives. Interestingly, the benzhydrol which has a substituent on meta- or para-position of one phenyl group,was resolved efficiently by complexation with bru … More cine. However, the benzhydrol which has an ortho-substituent was not. The structure dependence in the chiral recognition seems to be relating to so called the ortho-effect in organic chemistry in solution.The most interesting finding is the chiral recognition with cinchonidium chloride host. N-Benzoylcinchonidium chloride formed a 1:1 inclusion crystal with 2,2'-dihydroxy-1,1'-binaphthyl. By using the complexation, the latter was resolved very effectively. X-ray crystal structure analysis of the inclusion crystal showed that the hydroxyl group of the binaphthol forms a hydrogen bond network with the chloride anion. Interestingly, the N-benzylcinchonidium chloride was not effective for 10,10'-dihydroxy-9,9'-biphenanthryl which was, however, resolved easily by complexation with N-butylcinchonidium chloride.Some fruitful results were obtained in the study of enantioselective reaction in inclusion crystal. For example, photoirradiation of cyclohexenone and coumarin in their inclusion crystal with an optically active host compound gave optically active dimer. Photoirradiation of an inclusion crystal of acrylanilide with an optically active host gave optically active dihydroquinolinone derivative. The enantioselectivity of these photoreactions in inclusion crystals is almost perfect and optically almost pure enantiomers were obtained. Enantioselective Michael reaction in inclusion crystal was also successful.It was also disclosed that most chiral hosts work as chiral shift reagents. Less