Development of Inclusion Crystal for Asymmetric Synthesis

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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.