A Highly Efficient Method for the Copper‐Catalyzed Selective Synthesis of Diaryl Chalcogenides from Easily Available Chalcogen Sources

An efficient protocol for copper‐catalyzed C–S or C–Se bond formation between aryl iodides and easily available chalcogen sources leading to diaryl chalcogenides is reported. A variety of symmetrical diaryl sulfides and diaryl selenides were synthesized in good to excellent yields. Unsymmetrical diaryl sulfides were also obtained in moderate yields from two different aryl iodides by a one‐pot tandem process. This strategy was further successfully utilized for the synthesis of 2‐phenylbenzo[ b ]thiophene and of [1]benzothieno[3,2‐ b ]benzothiophene.