Palladium-catalyzed coupling reactions of bromothiophenes at the C-H bond adjacent to the sulfur atom with a new activator system, AgNO3/KF.

[reaction: see text] Bromothiophene derivatives react with aryl iodides catalyzed by a palladium complex in the presence of a silver(I) nitrate/potassium fluoride system to induce coupling at the C-H bond, while the carbon-bromine bond is intact. The produced coupling product bearing the C-Br bond allows further palladium-catalyzed C-C bond-forming reactions in reasonable yields.