Synthesis of Jellyfish-Type Macrocyclic Molecular Flask and Efficient Reaction Using the Molecular Flask

本课题拟拟合成笼型微环化合物等人工分子烧瓶，并利用类似于体内蛋白袋的分子烧瓶进行高效反应。蛋白质袋在体内是一个三维空穴，是利用氢键、π-电子相互作用、位阻斥力等作用的高效反应瓶。然后我们计划利用锰基氧化自由基大环化反应合成一种原始的笼型分子大环化合物。我们开发了锰基氧化自由基大环化反应，合成了多达二氢呋喃融合的50元大环化合物，该反应效率高，产率高。因此，我们研究了用锰基氧化自由基大环化反应合成原始笼型分子大环化合物。在合成年龄型大环化合物时，应进行以下检查：1)将客体有机化合物包被在笼型大环化合物的空腔中，2)利用氢键、π-电子相互作用和/或位阻排斥力将客体有机化合物和试剂固定在空腔中，3)客体有机化合物与空腔中试剂的高效反应，4)反应后产物的提取和分离，5)笼型大环化合物的回收和再利用。虽然没有合成笼型大环化合物，但制备了65元环苯型大环化合物。此外，还合成了9 ~ 18元的微二聚物。此外，还合成了许多新的客体有机分子。在不久的将来，我们将进一步研究所合成的环苯类大环化合物的功能。在此情况下，我们将实现笼型分子大环化合物的合成，并研究仿生分子烧瓶的功能能力。最后，我们将利用笼型分子大环化合物开发具有高度立体选择性的有机反应。少

This research project was proposed that an artificial molecular flask such as a cage-type mocrocyclic compound would be synthesized and a highly efficient reaction would be carried out using the molecular flask similar to that using a protein pocket in vivo. The protein pocket in vivo is a three-dimensional hole and it is an efficient reaction flask using hydrogen bond, π-electron interaction, steric repulsion, and so on. Then we planed to synthesize an original cage-type molecular macrocyclic compound using the manganese(III)-based oxidative radical macrocyclization reaction.We developed the manganese(III)-based oxidative radical macrocyclization reaction and the synthesis of up to dihydrofuran-fused fifty-membered macrocyclic compounds was achieved, This reaction is very efficient and the yield is also high. Therefore, we examined to synthesize the original cage-type molecular macrocyclic compounds using the manganese(III)-based oxidative radical macrocyclization reaction. When the c … More age-type macrocyclic compounds would be synthesized, it would be examined the following items ;1) the inclusion of a guest organic compound into the cavity of the cage-type macrocyclic compounds,2) the immobilization of the guest organic compound and reagents in the cavity using the hydrogen bond, π-electron interaction, and/or steric repulsion,3) the highly efficient reaction of the guest organic compound with reagents in the cavity,4) the extraction and separation of the products after the reaction,5) the recovery and reuse of the cage-type macrocyclic compounds.Although the cage-type macrocyclic compounds were not synthesized, sixty-five-membered cyclophene-type macrocyclic compounds were prepared. In addition, the synthesis of nine- to eighteen-membered microdiolides were achieved. Furthermore, many new guest organic molecules were synthesized.In the near future, we will plane to investigate the functional ability of the synthesized cyclophene-type macrocyclic compounds. In the event, we will achieve the synthesis of cage-type molecular macrocyclic compounds and investigate the functional ability for the biomimetic molecular flask. Finally, we will develop the highly stereoselective organic reactions using the cage-type molecular macrocyclic compounds. Less