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

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.