Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan.
Chemistry. 2010 Jul 5;16(25):7586-95. doi: 10.1002/chem.201000497.
Gambierol was isolated as a neurotoxin from the cultured cells of the ciguatera causative dinoflagellate Gambierdiscus toxicus and classified as a member of the polycyclic ether family of marine toxins. The structure consists of a ladder-shaped trans-fused octacyclic ring system that includes 18 stereogenic centers, two 1,3-diaxial dimethyl-substituted tetrahydropyranyl rings, and a partially conjugated triene side chain. The total synthesis of gambierol has been achieved by utilizing an oxiranyl anion strategy in an iterative manner. Synthetic highlights of this route include direct carbon-carbon formation on epoxides, sulfonyl-assisted 6-endo cyclization, and an expansion reaction of the tetrahydropyranyl rings to oxepanes to forge the polycyclic architecture of the target molecule.
吉百利醇是从导致雪卡鱼中毒的藻类冈比毒藻的培养细胞中分离出来的一种神经毒素，被归类为多环醚海洋毒素的一种。该结构由一个梯形反式稠合的八元环系统组成，包括 18 个手性中心、两个 1,3-二轴向二甲基取代的四氢吡喃环和一个部分共轭的三烯侧链。吉百利醇的全合成是通过利用环氧阴离子策略进行迭代实现的。该路线的合成亮点包括在环氧化物上直接形成碳-碳键、亚磺酰基辅助的 6-endo 环化以及四氢吡喃环的扩环反应，以形成目标分子的多环架构。
