One‐Pot Halogen Dance/Negishi Coupling of Dibromothiophenes for Regiocontrolled Synthesis of Multiply Arylated Thiophenes

One‐pot halogen dance/Negishi cross‐coupling of readily available 2,5‐dibromothiophenes is described. A lithium diisopropylamide (LDA)‐mediated halogen dance reaction resulted in the formation of thermodynamically stable α‐lithiodibromothiophenes, which were transmetalated with ZnCl₂ and subjected to Negishi cross‐coupling to provide the corresponding arylated dibromothiophenes in one pot. The resultant β‐bromo group was much less reactive than the remaining α‐bromo group, which was used in a one‐pot double Suzuki–Miyaura cross‐coupling, enabling facile synthesis of multiply arylated thiophenes.