A NEW DEVELOPMENT OF SYNTHETIC ORGANIC CHEMISTRY FOR BIOLOGICALLY ACTIVE NATURAL PRODUCTS OF MARINE ORIGINS

1)首次实现了从红藻Laurencia obtusa中分离的(+)-obtusenyne的全合成。此外，还合成了未经立体化学分离和立体化学未确定的两个异构体。这些结果导致了这些化合物的绝对构型的建立。2)建立了实现海洋来源的稠环聚醚化合物的生物合成途径的合成路线。最后，以相应的聚环氧基醇为模型，首次内切构筑了缩合的双环和三环醚化合物。3)建立了两种新的高效合成可聚合的二缩环醚的方法。4)对雪卡毒素的全合成进行了研究。合成策略是基于收敛过程来合成…进一步调整四个片段的大小，然后将它们组合起来，构建三个剩余的6-7元环醚体系(CD，GH，JK)。5)首次全合成了从红藻Polycavernosa tsudai中分离出来的可致人中毒的化合物Polycavernosa tsudai。6)开展了细鳞扇贝贝毒毒素全合成的研究。从而实现了普通BCDEF-环系统的一步构造。此外，通过模型实验建立了利用分子间Diels-Alder反应构建AG-环体系的策略。7)开展了由条斑扇贝引起的贝类中毒果胶毒素的全合成研究。结果，除C30位外，所有片段都能被构建。较少

1) The first total synthesis of (+)-obtusenyne isolated from a red alga, Laurencia obtusa, has been achieved. Furthermore, two isomers of obtusenyne, which had been isolated by None and undetermined stereochemically, were totally synthesized. These results led to establishment of the absolute configuration of these compounds.2) The synthetic route has been established toward realization of the proposed biosynthetic pathway for condensed cyclic polyether compounds of marine sources. Eventually, construction of the condensed bicyclic and tricyclic ether compounds were carried out firstly in endo-fashions starting from the corresponding polyepoxy alcohols as the models.3) Two new efficient methods have been established in order to construct convergently two-condensed cyclic ethers.4) The synthetic studies were developed toward the total synthesis of ciguatoxin which is the causative compound for ciguatera intoxication. The synthetic strategy was based on the convergent procedure to synthe … More size the four respective fragments and then to combine them constructing three residual 6-7-membered cyclic ether systems (CD,GH,JK). The synthesis of the CD and JK ring systems has been already achieved.5) The first total synthesis of polycavernoside A isolated from a red alga, Polycavernosa tsudai, regarding as a causative compound for human intoxication, has been achieved. Furthermore, the structure-biological activity relationship has been clarified.6) The study toward the total synthesis of pinnatoxins causing shell-fish poisoning originated from Pinna attenuata has been developed. Resultingly, the 1-step construction of the common BCDEF-ring system has been achieved. Furthermore, the strategy for construction of the AG-ring system has been established using an intermolecular Diels-Alder reaction by the model experiments.7) The study toward the total synthesis of pectenotoxins causing shell-fish poisoning originated from Patinopecten yessoensis has been developed. Resultingly, all the fragments were able to be constructed except the C30 position. Less