Photocatalyzed ditrifluoromethylthiolation of alkenes with CF 3 SO 2 Na

Since the first report of sodium trifluoromethanesulfinate (CF 3 SO 2 Na) as an electrophilic trifluoromethylthiolation reagent in 2015, there has been no breakthrough in research in this field. Herein, we disclose an unprecedented usage of CF 3 SO 2 Na as a radical trifluoromethylthiolation reagent. A photocatalyzed ditrifluoromethylthiolation of alkenes with CF 3 SO 2 Na in the presence of PPh 3 and catalytic copper has been developed. Interestingly, either Ir[(p-Fppy) 2 (bpy)]PF 6 or Ir(ppy) 3 could facilitate this transformation. Mechanistic studies indicate that initiation of the radical chain proceeded via two different photocatalytic quenching mechanisms. This protocol provides a practical method for the construction of diverse vicinal ditrifluoromethylthiolated compounds.