Knoevenagel-type condensation of 1,3-bis(phenylsulfonyl)propene with aldehydes provided electron-deficient dienes, 1,3-bis(phenylsulfonyl)butadiene derivatives, and one of these dienes, 4-[3,4-(methylenedioxy)]phenyl derivative was applied to Michael-type addition with enamines to form six-membered ring systems.