Stereoselective Syntheses of trans -Anhydromevalonic Acid and trans -Anhydromevalonyl Group-Containing Natural Products.

Collective total syntheses of trans -anhydromevalonic acid (tAHMA) and trans -anhydromevalonyl (tAHM) group-containing natural products (pestalotiopin A, pestalotiopamide C, pestalotiopamide D, farinomalein E, eleutherazine B, and trichocyclodipeptide A) were achieved using tAHMA esters as key intermediates. To this end, tAHMA tert -butyl ester was newly prepared by Z -vinyltosylation of tert -butyl 3-oxo-5-((triisopropylsilyl)oxy)pentanoate followed by the Negishi cross-coupling reaction with Me 2 Zn. tAHMA esters were converted to the target natural products via esterification or amidation. Comparison of the spectroscopic data of synthetic and natural products confirmed the E -configuration of the tAHM moieties in the natural products.