Development of Inclusion Crystal for Asymmetric Synthesis

设计了酒石酸衍生物、炔醇、双β-萘酚等手性主体化合物，发现它们是固态不对称合成的良好主体。利用新开发的主体化合物进行了一些新的不对称合成。首先，手性主体化合物与环己烯酮的包合物与亲双烯体的反应在固态下有效地进行，得到了光学活性的Michael加成产物。该反应具有良好的对映异构性，可得到80%cc左右的光学活性产物。其次，在包合物晶体中也发生了对映选择性的Witting反应，可得到光学活性的烯烃产物。第三，在光学活性主体与烯烃的包合物中，实现了非常有效的对映选择性（2+2）光加成反应。第四，简单螺烯-N-甲基-3，4-双（二苯基亚甲基）琥珀酰亚胺形成了琥珀酰亚胺分子以手性形式排列的手性晶体，固态手性螺烯晶体的光照射得到了光学活性的光反应产物，手性主体和氧代酰胺客体在固态混合得到了后者分子以手性形式排列的包合物。包合物的辐照得到光学活性的β-内酰胺衍生物。一些氧代酰胺化合物也形成手性晶体，其中对称的氧代酰胺分子通过围绕两个CO基团之间的单键扭转而以手性形式排列。在固态的手性晶体的光照射得到高光学纯度的光学活性β-内酰胺衍生物。最令人感兴趣的发现是固态的氧代酰胺的对称分子的运动和这些分子在如上所述的包合络合物中以手性形式的取代。

Some chiral host compounds such as tartaric acid derivatives, acetylenic alcohols and bis-beta-naphthols were designed and these were found to be good host for asymmetric synthesis in the solid state. Some new asymmetric syntheses by using the newly developed hosts have aslo been established. Firstly, reaction of an inclusion complex of chiral host compound and cyclohexenone with dienophiles proceeded efficiently in the solid state and optically active Michael addition products were obtained. Enantiosoloctivity of the reaction was quite good and optically active products of about 80% cc were obtained.Secondly, enantioselective Witting reaction also occurred in an inclusion complex crystal to give optically active olefnic products. Thirdly, very efficient enantioselective (2+2) photoaddition reactions were accomplished in an inclusion complex of optically active host and olefin. Fourthly, a simple helicene, N-methyl-3,4-bis (diphenylmethylene) succimide formed a chiral crystal in which the succimide molecules are arranged in a chiral form, and photoirradiation of the chiral helicene crystal in the solid state gave optically active photoreaction product.Mixing of chiral host and oxoamide guest in the solid state gave an inclusion complex in which the latter molecules are arranged in a chiral form. Irradiation of the inclusion complex gave optically active beta-lactam derivatives. Some oxoamide compounds also formed chiral crystals in which symmetrical oxoamide molecules are arranged in a chiral form by twisting around the single bond between two CO groups. Photoirradiation of the chiral crystal in the solid state gave optically active beta-lactam derivatives of high optical purity. The most interesting finding is a movement of symmerical molecules of the oxoamide in the solid state and an arrangedment of these in a chiral form in an inclusion complex as described above.