A new pathway towards α-fluoro-β-arylvinyl sulfones was elaborated. The reaction of β- bromo-β-fluorostyrenes with sodium 4-methylphenylsulfinate proceeds with maximum 94: 6 stereoselectivity and 72–90% yields. The formed α-fluoro-β-arylvinyl sulfones were found to be good dienophiles for Diels–Alder reactions with simple 1, 3-dienes. From corresponding (E)-configured dienophiles and cyclopentadiene, cycloadducts bearing the fluorine ...