Vinylsulfonates prepared from hydroxyalkyl substituted cycloalka-1,3-dienes and acyclic 1,3-dienes by esterification with vinylsulfonyl chloride cycloadd to δ-sultones at temperatures ranging from 0 °C to reflux in toluene. High diastereoselectivity is observed for substrates 2 featuring a cyclic 1,3-diene moiety, whereas a substituent R 2 larger than hydrogen is necessary to achieve good to excellent levels of stereocontrol for substrates 9 possessing an acyclic 1,3-diene unit. Oxidative desulfurization of the resultant sultones via borylation and subsequent peracid treatment yields hydroxy ketones, thus establishing vinylsulfonyl chloride as a regio- and stereoselectivity reacting ketene equivalent for the intramolecular Diels-Alder cycloaddition.