The stereoselective total syntheses of naturally occurring bioactive 2,6-epoxydiarylheptanoids tsaokopyranols (–)-E, (–)-L, (+)-M, (+)-jughopnin J, and (–)-engelheptanoxide A have been accomplished in 4–6 steps starting from a chiral epoxide utilizing dehydrogenative cycloetherification and epimerization of trans- to cis-2-alkyl-6-aryl-3,6-dihydro-2H-pyran framework as the key steps. The absolute configuration of natural tsaokopyranol L was revised.
