Total Synthesis and Stereochemical Confirmation of Heliolactone.

Until now, the relative stereochemistry of the noncanonical strigolactone, heliolactone, has remained ambiguous. The total synthesis of heliolactone is described, with the key bond-forming event being a Stille cross-coupling that relied upon a reversal of the nucleophile-electrophile coupling partners. Spectroscopic analysis of synthetic heliolactone (and other stereoisomers) and comparisons with the isolated material enabled the absolute and relative stereochemistry of heliolactone to be secured.