Absolute configuration of amphidinol 3, the first complete structure determination from amphidinol homologues: Application of a new configuration analysis based on carbon-hydrogen spin-coupling constants
Absolute configuration of amphidinol 3, the first complete structure determination from amphidinol homologues: Application of a new configuration analysis based on carbon-hydrogen spin-coupling constants
复制标题
DOI：
10.1021/ja983655x
复制
发表时间：
1999-02-03
影响因子：
15
通讯作者：
Tachibana, K
中科院分区：
文献类型：
--
作者：
Murata, M;Matsuoka, S;Tachibana, K
甲藻是一种原始的单细胞藻类，是结构和生物学上有趣的天然产物的丰富来源，如冈田酸、短鞭藻毒素、雪卡毒素和舞毒蛾毒素。在这些聚醚环状化合物中，氨杂环醇是独特的甲藻代谢物，因为它们主要由线性多羟基结构组成。该组的第一个成员是由Yasumoto的小组从甲藻Amphidinium klebsii中分离出来的，作为一种有效的抗真菌物质。[1a]一系列的同系物[1b]、[1c]后来在同一属中被发现，小林的研究小组报告了密切相关的化合物--木犀草酚。2这些长链多羟基化合物可能是立体结构解析中最具挑战性的目标之一，因为手性中心分散在灵活的非环状结构中。因此，很少有人知道的Ampidinols.We最近开发的J-为基础的配置分析，3这已被证明是一个强大的工具，立体化学测定的非环状结构的立体中心的性质。3b在该方法中，手性中心之间的1，2-非对映异构体关系通过使用自旋耦合常数（3 JH，H和2，3 JC，H，例如，参见图1c中的2 JC，H）在由顺式和苏式构型产生的六种可能性中选择正确的交错旋转异构体来确定。3a在本文中，我们报道了amphidinol 3（1），amphidinol家族的一个代表性同系物的完整构型，主要是使用这种基于J的方法。
Dinoflagellates, a type of primitive unicellular algae, are a rich source of structurally and biologically intriguing natural products; eg, okadaic acid, brevetoxins, ciguatoxins, and maitotoxin. Among these polyether-cyclic compounds, amphidinols are unique dinoflagellate metabolites since they are primarily made up of linear polyhydroxy structures. The first member of this group was isolated from the dinoflagellate Amphidinium klebsii as a potent antifungal substance by Yasumoto’s group. 1a A series of homologues1b, c has since been found in the same genus, and Kobayashi’s group reported closely related compounds, luteophanols. 2 These long-chain polyhydroxy compounds may be one of the most challenging targets for stereostructural elucidation since chiral centers are scattered over a flexible acyclic structure. Thus, little is known of the nature of the stereogenic centers in amphidinols.We recently developed J-based configuration analysis, 3 which has been proven to be a powerful tool for the stereochemical determination of acyclic structures. 3b In this method, 1, 2-diastereomeric relationships between chiral centers are determined by choosing a correct staggered rotamer among six possibilities arising from erythro and threo configurations using spin-coupling constants (3JH, H and 2, 3JC, H, eg, see Figure 1c for 2JC, H). 3a In this paper, we report the complete configuration of amphidinol 3 (1), a representative homologue of the amphidinol family, mainly using this J-based method.