Synthesis of Multifluoromethylated γ‐Sultines by a Photoinduced Radical Addition–Polar Cyclization

Despite the significance of sultines in synthesis, medicine, and materials science, the chemistry of sultines has remained unexplored due to their inaccessibility. Herein, we demonstrate the development of a photoredox‐catalyzed multifluoromethyl radical addition/SO2 incorporation/polar cyclization cascade approach to multifluoromethylated γ‐sultines. The reactions proceed by single electron transfer induced multifluoromethyl radical addition to an alkene followed by SO2 incorporation, and single‐electron reduction for polar 5‐exo‐tet cyclization. Key to the success of the protocol is the use of easily oxidizable multifluoroalkanesulfinates as bifunctional reagents. The reactions proceed with excellent functional‐group tolerance to deliver γ‐sultines in moderate to excellent yields. A photoredox‐catalyzed multifluoromethyl radical addition/SO2 incorporation/polar cyclization cascade approach to multifluoromethylated γ‐sultines has been developed. The reaction proceeds with broad functional‐group tolerance and good yields. Key to the success of the protocol is use of oxidizable multifluoroalkanesulfinates as bifunctional reagents.