Synthesis and Stereochemistry of the C30-C63 Section of Karlotoxin 2
Synthesis and Stereochemistry of the C30-C63 Section of Karlotoxin 2
复制标题
DOI：
10.1002/ajoc.202000181
复制
发表时间：
2020-09-02
影响因子：
2.7
通讯作者：
Oishi，Tohru
中科院分区：
文献类型：
--
作者：
Umeno，Keitaro;Oishi，Tohru
Karlotoxin 2 (KmTx2) 是从甲藻 Karlodinium veneficum 中分离出来的海洋天然产物。通过NMR分析结合天然产物的降解确定了KmTx2的绝对构型，并通过计算分析修正了C49处的绝对构型。另一方面，我们通过比较 AM3 的部分结构和全合成的 NMR 数据，报道了与 KmTx2 结构相似的 amphidinol 3 (AM3) 的绝对构型的修正。在本文中，我们报告了KmTx2对应于C30−C63部分的部分结构以及C37、C41−C43和C45−C49处的非对映异构体的合成，这是在AM3的修改结构的基础上假设提出的。合成样品与天然产物的NMR数据的比较表明KmTx2的绝对构型被修改为37R、41R、42R、43R、45R、46R、47R、48S和49S。
Karlotoxin 2 (KmTx2) is a marine natural product isolated from the dinoflagellateKarlodinium veneficum. The absolute configuration of KmTx2 was determined by NMR analysis in combination with degradation of the natural product, and the absolute configuration at C49 was revised by computational analysis. On the other hand, we reported revision of the absolute configuration of amphidinol 3 (AM3), whose structure is similar to that of KmTx2, by comparing NMR data of the synthesized partial structures and total synthesis of AM3. In this paper, we report the synthesis of the partial structures of KmTx2 corresponding to the C30−C63 section, and the diastereomer at C37, C41−C43, and C45−C49, which is hypothetically proposed on the basis of the revised structure of AM3. Comparison of the NMR data of the synthetic specimens with those of the natural product suggested that the absolute configuration of KmTx2 is revised to be 37R, 41R, 42R, 43R, 45R, 46R, 47R, 48S, and 49S.