With these optimized conditions in hands, we next studied the scope of the hydrotrifluoromethylation of styrenes with the Langlois reagent. Ortho-substituted styrene allowed the formation of the desired product in 55% yield (product 3ab). The presence of diphenylphosphine in para position was also tolerated under our conditions and the desired product 3pb was obtained in 50% yield. The use of estrone derivatives allowed to obtain the desired product 3nc with a good yield of 65%. To demonstrate further the utility of this new methodology we decided to investigate the same scope of different sulfinate salts as used in the above-described synthesis of the fluorinated hexestrol derivatives. Once more, all tested sulfinates were effective under our reaction conditions and the desired products were obtained in moderate to very good yield either starting with simple styrene or the estrone derivatives. As a major outcome of this work, new compounds containing CF2H, CFH2, MeCF2 and CF2ArBr could be obtained for the first time under our protocol demonstrating again the robustness of the developed methodology. Scheme 2. Reaction scope. for the hydrotrifluoromethylation of styrene. Reactions were performed with styrene derivatives 1 (0.2 mmol, 1 equiv.), RFSO2Na (0.4 mmol, 2 equiv.), PC2 (2 mol%) and DMSO (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.