Highly regio- and enantioselective allylic alkylation of fluorobis(phenylsulfonyl)methane (FBSM) has been realized by [Ir(COD)Cl]2/phosphoramidite, affording enantiopure fluorobis(phenylsulfonyl)methylated compounds bearing a terminal alkene, which could be converted to monofluoro-methylated ibuprofen in just two steps without loss of the optical purity (95% ee).