Direct Synthesis of Monofluoromethylthioesters from Acyl Chlorides with Elemental Sulfur and Fluoroiodomethane

We report an unprecedented Ni‐catalyzed direct monofluoromethylthiolation of acyl chlorides, in situ generated from carboxylic acids, with elemental sulfur (S 8 ) as the S source and fluoroiodomethane (ICH 2 F) as the CH 2 F radical source to produce a series of monofluoromethylthioesters in moderate to good yields. This approach features excellent functional group tolerance and broad substrate scope. Additionally, the late‐stage monofluoromethylthiolation of complex bioactive molecules can also be accomplished using this method.