A biosynthetically-inspired synthesis of the tetrahydrofuran core of obtusallenes II and IV.

Sharpless asymmetric dihydroxylation was regioselective for the trans olefin in an E vs Z vs terminal triene substrate. To test a biosynthetic hypothesis, the resulting diol underwent diastereoselective bromoetherification to provide the des-chloro core of marine natural products obtusallenes II and IV. Alternatively, anionic chloride ring-opening of a Z-beta,gamma-unsaturated epoxide gave separable regioisomeric halohydrins. Bromoetherification gave the fully elaborated core of obtusallenes II and IV with all of the relative stereochemistry correctly set.