A stereoselective synthesis of (E)-α-hydroxy-1, 3-dienes, by thermal extrusion from adducts of 2, 5-dihydrothiophene S, S-dioxide (1) with aldehydes and ketones, is presented and its extension to the synthesis of the dienone,(E)-tagetone, and of a 1, 3, 5-triene system, is illustrated.