Intramolecular Diels-Alder Reaction of Vinylsulfonates Derived from Hydroxyalkyl Substituted 1,3-Dienes and Oxidative Desulfurization of the Resultant Sultones

Article abstract of DOI:10.1016/0040-4020(94)00969-2

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 deg C to reflux in toluene.High diastereoselectivity is observed for substrates 2 featuring a cyclic 1,3-diene moiety, whereas a substituent R² 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 stereoselectively reacting ketene equivalent for the intramolecular Diels-Alder cycloaddition.