Iron(III) Chloride‐Catalyzed Direct Sulfonylation of Alcohols with Sodium Arenesulfinates

A new protocol for the direct sulfonylation of benzylic, allylic and homoallylic alcohols with sodium arenesulfinates is described by using iron(III) chloride as a catalyst and chlorotrimethylsilane as an additive. This method requires no pre-activation of alcohols. Surprisingly in the reaction with homoallyl alcohols nucleophilic addition of sulfinate anion, occurs at the terminal double bond instead of nucleophic substitution at the alcohol.