Alkali Metal- and Acid-Catalyzed Interconversion of Goniodomin A with Congeners B and C

Constance M. Harris, Bernd Krock, Urban Tillmann, Craig J. Tainter, Donald F. Stec, Aaron J. C. Andersen, Thomas O. Larsen, Kimberly S. Reece, Thomas M. Harris*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review


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.
Original languageEnglish
JournalJournal of Natural Products
Issue number9
Pages (from-to)2554-2567
Number of pages14
Publication statusPublished - 2021


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