Heterogeneously Catalyzed Direct CH Thiolation of Heteroarenes

The first general methodology for the direct thiolation of electron‐rich heteroarenes was developed by employing Pd/Al₂O₃, a recoverable and commercially available heterogeneous catalyst, and CuCl₂. This method represents an operationally simple approach for the synthesis of these valuable compounds. Preliminary mechanistic studies indicate a heterogeneous catalytic system, in which both metals play a complementary role in the formation of the thiolated products.