2,3‐Disubstituted Benzo[b]thiophenes from Diarylalkynes via Electrophilic Addition‐Cyclization and Palladium‐Catalyzed Cross‐Coupling

Diarylalkynes are readily transformed in 3‐chlorobenzo[b]thiophenes in a two‐step electrophilic addition‐cyclization procedure that runs highly efficiently in solution or in the solid phase. The heteroaromatic carbon‐chlorine bond participates in palladium‐catalyzed Suzuki–Miyaura or Buchwald–Hartwig cross‐couplings to give, in a single step, 2,3‐disubstituted derivatives of pharmacological relevance .