Alkali Metal- and Acid-Catalyzed Interconversion of Goniodomin A with Congeners B and C,Journal of Natural Products

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Alkali Metal- and Acid-Catalyzed Interconversion of Goniodomin A with Congeners B and C
Journal of Natural Products ( IF 3.3 ) Pub Date : 2021-09-14 , DOI: 10.1021/acs.jnatprod.1c00586
Constance M Harris ₁ , Bernd Krock ₂ , Urban Tillmann ₂ , Craig J Tainter ₁ , Donald F Stec ₁ , Aaron J C Andersen ₃ , Thomas O Larsen ₃ , Kimberly S Reece ₄ , Thomas M Harris _{1,

4}

Affiliation

Goniodomin A (GDA, 1) is a phycotoxin produced by at least four species of Alexandrium dinoflagellates that are found globally in brackish estuaries and lagoons. It is a linear polyketide with six oxygen heterocyclic rings that is cyclized into a macrocyclic structure via lactone formation. Two of the oxygen heterocycles in 1 comprise a spiro-bis-pyran, whereas goniodomin B (GDB) contains a 2,7-dioxabicyclo[3.3.1]nonane ring system fused to a pyran. When H₂O is present, 1 undergoes facile conversion to isomer GDB and to an α,β-unsaturated ketone, goniodomin C (GDC, 7). GDB and GDC can be formed from GDA by cleavage of the spiro-bis-pyran ring system. GDA, but not GDB or GDC, forms a crown ether-type complex with K⁺. Equilibration of GDA with GDB and GDC is observed in the presence of H⁺ and of Na⁺, but the equilibrated mixtures revert to GDA upon addition of K⁺. Structural differences have been found between the K⁺ and Na⁺ complexes. The association of GDA with K⁺ is strong, while that with Na⁺ is weak. The K⁺ complex has a compact, well-defined structure, whereas Na⁺ complexes are an ill-defined mixture of species. Analyses of in vitro A. monilatum and A. hiranoi cultures indicate that only GDA is present in the cells; GDB and GDC appear to be postharvest transformation products.

中文翻译：

碱金属和酸催化的 Goniodomin A 与同源物 B 和 C 的互变

Goniodomin A (GDA, 1 ) 是一种藻毒素，由至少四种在全球咸淡水河口和泻湖中发现的亚历山大鞭毛藻产生。它是具有六个氧杂环的线性聚酮化合物，通过内酯形成环化成大环结构。中的氧杂环的两个1包括螺-双-吡喃，而goniodomin B（GDB）包含稠合到一个吡喃2,7-二氧杂双环[3.3.1]壬烷环系。当 H ₂ O 存在时，1容易转化为异构体 GDB 和 α,β-不饱和酮，goniodomin C（GDC，7）。GDB 和 GDC 可以通过螺-双-吡喃环系统的裂解从 GDA 形成。GDA，但不是 GDB 或 GDC，与 K ⁺形成冠醚型配合物。在 H ⁺和 Na ⁺存在下观察到 GDA 与 GDB 和 GDC的平衡，但平衡的混合物在添加 K ⁺后恢复为 GDA 。已发现 K ⁺和 Na ⁺配合物之间存在结构差异。GDA与K ⁺的关联强，而与Na ⁺的关联弱。K ⁺复合物具有紧凑、明确的结构，而 Na ⁺复合物是不明确的物种混合物。体外分析A. monilatum和A. hiranoi培养物表明细胞中仅存在 GDA；GDB 和 GDC 似乎是收获后转化产品。

更新日期：2021-09-24

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