Stereoselective synthesis of enynones via base-catalyzed isomerization of 1,5-disubstituted-2,4-pentadiynyl silyl ethers or their alcohol derivatives

1,5-Disubstituted-2,4-pentadiynyl silyl ethers undergo smooth desilylative isomerization to afford cis-enynones as major products with moderate stereoselectivities in the presence of a catalytic amount of KOtBu or DBU. While the isomerization reactions of their alcohol derivatives catalyzed by KOH, KOtBu or NaH take place efficiently to produce trans-enynones with high stereoselectivities. These reactions provide convenient and practical routes for the synthesis of enynones with a wide range of substitution groups.