Base Catalysis Enables Access to α,α-Difluoroalkylthioethers

A nucleophilic addition reaction of aryl thiols to readily available beta,beta-difluorostyrenes provides alpha,alpha-difluoroalkylthioethers: The reaction proceeds through an unstable anionic intermediate, prone to eliminate fluoride and generate alpha-fluorovinylthioethers: However, the use of base catalysis overcomes the facile beta-fluoride elimination, generating alpha,alpha-difluoroalkylthioethers in excellent yields and selectivities.