Selfassembly of Molecules in Crystal and Its Application to Selective Synthesis

晶体分子自组装及其在选择性合成中的应用

基本信息

批准号：
03303002
负责人：
TODA Fumio
金额：
$ 6.21万
依托单位：
Ehime University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

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

将主体-寻求包合物晶体中的手性识别应用于客体化合物的光学拆分，发现衍生自酒石酸的光学活性主体化合物可有效地通过手性识别来光学拆分各种客体化合物。旋光二乙炔醇主体化合物微妙地取决于其化学结构，例如，尽管旋光二乙炔醇主体对于前列腺素合成的重要起始材料羟基环戊烯酮的拆分无效。在两个炔基之间具有对位二取代苯基的二乙炔醇主体化合物对于拆分效果非常好。然而，发现马钱子碱等生物碱对于拆分一个苯基的间位或对位二苯甲醇衍生物是有效的。基团，通过与布鲁…更多电影络合被有效地解决，然而，二苯甲醇具有一个。手性识别中的结构依赖性似乎与溶液中有机化学中的邻位效应有关。最有趣的发现是与氯化辛可尼鎓主体的手性识别形成1。：1与2,2'-二羟基-1,1'-联萘的包合物晶体通过使用络合作用，可以非常有效地解析后者的X射线晶体结构。包合物晶体表明，联萘酚的羟基与氯离子形成氢键网络，很容易与N-丁基辛可尼鎓氯化物络合。在包合物晶体的对映选择性反应的研究中取得了一些丰硕的成果。用旋光主体化合物对它们的包合物晶体进行光照射，得到旋光二聚体。用旋光主体化合物对丙烯酰苯胺包合物晶体进行光辐照，得到旋光二氢喹啉酮衍生物。包合物晶体中的这些光反应的对映选择性几乎是完美的。包合物晶体中的对映选择性迈克尔反应也获得了成功。还公开了大多数。手性主体作为手性位移试剂。