Metal‐Free Direct Nucleophilic Perfluoroalkylthiolation with Perfluoroalkanesulfenamides

Abstract We report herein a practical method to generate CF 3 S − and R F S − anions in situ from shelf‐stable reagents, which were initially designed for electrophilic reactions. With an “iodide activation” step, these in situ released anions can directly participate in metal‐free nucleophilic substitution reactions with the loss of various leaving groups. Our method is compatible with various functional groups and provides good yields. With this strategy, the first direct nucleophilic perfluoroalkylthiolation reactions have been described.