Self-Assembly of Molecules in Crystal and Its Application to Selective Organic Synthesis

人们发现，分子在晶体中的自组装并不总是足以进行选择性反应。然而，我们发现，当反应物分子与主体分子组装在一起时，前者排列规则，固相反应选择性地进行。例如，将N-苯甲酰甲基-β-戊内酰胺(2)与酒石酸衍生的光学活性主体(1)1：1的包合物粉末在水悬浮液中搅拌，得到光学几乎纯的双环三角洲-戊内酰胺醇。X-射线晶体结构分析表明，2和1分子自组装形成1：1的包合物，在包合物中发生精确的手性识别。根据手性识别，控制试剂从反应物的前后侧的攻击，得到单一的产物。还制备了2和1的各种衍生物的包合物晶体，它们的光反应得到了光学纯的光环化产物。

It was found that self-assembly of molecules in crystal is not always adequate for a selective reaction. However, we found that when molecules of reactant are assembled together with host molecules, the former are arranged regularly and the solid state reaction proceeds selectively.For example, photoirradiation of a 1 : 1 inclusion complex powder of N-benzoylmethyl-delta-valerolactam (2) and the optically active host (1) which had been derived from tartaric acid, in a water suspension under stirring gave optically almost pure bicyclic delta-valerolactam alcohol. X-ray crystal structure analysis of the inclusion complex showed that molecules of 2 and 1 are self-assembled to form 1 : 1 inclusion complex in which precise chiral recognition occurs. According to the chiral recognition, attack of reagent from the front and rear side of the reactant is controlled and single product is obtained. Inclusion crystals of various derivatives of 2 with 1 were also prepared and their photoreactions gave optically pure photocyclization products.