Synthesis and relative stereochemistry of the A- and F-rings of goniodomin A

The synthesis of the A- and F-rings of goniodomin A (1), which is a stereochemically unidentified antifungal agent isolated from dinoflagellate Alexandrium hiranoi, was performed to determine of the relative stereochemistry of these parts. The relative stereochemistry of the A- and F-rings was first deduced from Murakami's NMR data, and model compounds corresponding to these parts were then synthesized. The synthetic A-ring model, of which the structure was established by X-ray crystallographic analysis, showed good agreement with the natural A-ring on the basis of J and NOE behavior in the H-1 NMR spectroscopy. The chemical shifts in H-1 and C-13 NMR specta and J(32-OH-H33) of the synthetic F-ring model having a 33S,34R configuration also agreed with those of the F-ring of 1. Thus, the relative stereochemistry of the A- and F-rings of 1 was elucidated.