With the best conditions in hand, we turned our attention to study the scope of the reaction. Styrenes substituted with electron donating groups including methyl, methoxy or acetoxy were effectively transformed under our conditions and the desired products were obtained in good to excellent yields, up to 85% (Scheme 1, compounds 2a-c). Steric hindrance was also tolerated, as the presence of methyl in ortho position of the styrene allow to obtain the desired product in an excellent yield of 88% (Scheme 1, compound 2b). Interestingly, the meso form of compound 2e turned out to be solid. Hence, X-ray analysis allowed us to fully confirm the expected structure of 2e (Scheme 1). Afterwards, the tolerance of the reaction towards the presence of halogen substituents was also investigated, either using a C(Csp 3 )-Cl or C(Csp 2 )-Cl, Br or F containing reactants. Good to excellent yields were obtained with halogenated styrenes substituted in para position (compounds 2f-i). 2-Bromostyrene was also effective under our reaction conditions and the desired product was obtained in a synthetically useful yield of 30% (compound 2j). We showed that our procedure also tolerates electron deficient styrenes: both 4-cyanostyrene and 4trifluoromethylstyrene allowed the formation of the corresponding hexestrol derivatives in good to excellent yield (compounds 2k & 2l). Heterocyclic 2-vinylpyridine also allows to obtain the desired product albeit in a low yield of 30% (2m). Interestingly, we also demonstrated that our protocol is tolerant to complex molecular structures and estrone derivatives 2n was obtained in 45% yield. Moreover, 1,1disubstituted styrene could also be smoothly transformed to the desired product 2o in excellent yield of 80%. Then, we turned our attention to study the impact of the starting sulfinate on the reaction outcome (Scheme 1), since the use of a variety of different sulfinate precursors opens many perspectives on a molecular diversity of accessible structures point of view. Indeed, we demonstrated that hexestrol derivatives containing CF2H, CH2F as well as MeCF2 and p-BrBnCF2 could also be obtained in good to excellent yield (Scheme 1, 2ea-2ec). Once again, the same protocol could be extended to complex molecular structures (Scheme 1, 2na-2nc). Scheme 1. Reaction scope.for the synthesis of fluoroalkylated hexestrol derivatives. Reactions were performed with styrene derivatives 1 (0.2 mmol, 1 equiv.), RFSO2Na (0.2 mmol, 1 equiv.), PC1 (2 mol%) and ACN (2 mL). The reaction mixture was stirred at room temperature for 16 hours under blue LED irradiation and inert conditions. Yields shown are those of isolated products; yields determined by F NMR spectroscopy with PhOCF3 as internal standard are shown in parentheses. meso and d,l enantiomers ratio was calculated from the crude.