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Development of Inclusion Crystal for Asymmetric Synthesis

不对称合成包合物晶体的开发

基本信息

批准号：
05554020
负责人：
TODA Fumio
金额：
$ 9.98万
依托单位：
Ehime University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

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.

设计了酒石酸衍生物、乙炔醇和双-萘酚等手性宿主化合物，发现它们是固体不对称合成的良好宿主。利用新开发的寄主还建立了一些新的不对称合成方法。首先，手性主体化合物和环己酮包合物与亲二烯试剂在固态条件下进行了高效反应，得到了具有光学活性的Michael加成产物。该反应的对映性较好，产物的旋光性约为80%。其次，包合物晶体中也发生了对映选择性Witting反应，生成了具有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，简单螺旋烯n -甲基-3,4-双（二苯基亚甲基）丁酰亚胺形成手性晶体，其中丁酰亚胺分子以手性形式排列，对固态的手性螺旋烯晶体进行光照射得到光学活性光反应产物。手性宿主和氧化酰胺客体在固体状态下混合得到包合物，后者分子以手性形式排列。包合物的辐照得到光学活性的β -内酰胺衍生物。一些氧酰胺化合物也形成手性晶体，其中对称的氧酰胺分子通过缠绕两个CO基团之间的单键以手性形式排列。手性晶体在固体状态下的光照射可以得到光学纯度高的光学活性β -内酰胺衍生物。最有趣的发现是氧酰胺的对称分子在固体状态下的运动，以及如上所述的在包合物中的手性排列。