Total Synthesis of Gambierol by Using Oxiranyl Anions
Total Synthesis of Gambierol by Using Oxiranyl Anions
复制标题
环氧乙烷基阴离子全合成甘比尔醇
DOI：
10.1002/chem.201000497
复制
发表时间：
2010
期刊：
影响因子：
--
通讯作者：
Yuji Mori
中科院分区：
文献类型：
--
作者：
Hiroki Furuta;Yuki Hasegawa;Mariko Hase;Yuji Mori
甘比埃罗是从引起甲藻的甲藻培养细胞中分离得到的一种神经毒素，属于海洋多环醚类毒素。该结构由一个梯形的反式稠合八环系统组成，该系统包括18个立体生成中心、两个1，3-二轴二甲基四氢吡喃环和一个部分共轭的三烯侧链。通过使用氧杂环氧基阴离子策略，以迭代的方式实现了冈比亚贝罗的全合成。这条路线的合成重点包括环氧化物上的直接碳-碳形成，磺酰基辅助的6-内环化，以及四氢吡喃环到氧环烷的膨胀反应，以锻造目标分子的多环结构。
Gambierol was isolated as a neurotoxin from the cultured cells of the ciguatera causative dinoflagellateGambierdiscus toxicusand classified as a member of the polycyclic ether family of marine toxins. The structure consists of a ladder‐shapedtrans‐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‐endocyclization, and an expansion reaction of the tetrahydropyranyl rings to oxepanes to forge the polycyclic architecture of the target molecule.