Rhodium‐Catalyzed Annulative Coupling of 3‐Phenylthiophenes with Alkynes Involving Double C‐H Bond Cleavages

Double CH bond activation took place efficiently upon treatment of 3-phenylthiophenes with alkynes in the presence of a rhodium catalyst and a copper salt oxidant to form the corresponding naphthothiophene derivatives. Dehydrogenative coupling with alkenes was also found to occur on the phenyl moiety rather than the thiophene ring. These reactions provide straightforward synthetic methods for π-conjugated molecules involving a thiophene unit from readily available, simple building blocks.