New one-pot procedures for the synthetic elaboration of sultones with concomitant desulfurization have been developed. Alkylation of α-metalated allylic sultones prepared either by deprotonation, radical cyclization/transmetalation or conjugate 1,6-addition with iodomethylmagnesium chloride is immediately followed by β-elimination to give highly substituted sulfur-free methylidene cyclohexenes. An advanced intermediate for the synthesis of several 1,10-seco-eudesmanolides is efficiently available by this new method.