The Reaction of Aryl Thiols or Thioureas with o‐Diiodoarenes/NaH to Access o‐Iodoaryl Thioethers

Abstract Herein we report a method for the synthesis of thioethers by forging C(aryl)‐S bond via an aryne mechanism. The active aryne species can be generated from o ‐diiodoarenes and NaH in THF at room temperature, then lead to the arylations of a wide range of aryl thiols and thioureas. Different from transition metal‐catalyzed cross‐coupling reactions, no disubstituted byproduct is formed in our protocol. The o ‐iodoaryl thioether products are intermediates that could be transformed into pharmaceutically interesting molecules.