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

Abstract 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/SO 2 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 SO 2 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.