WCl 6 /DMF as a new reagent system for the phosphine-free Pd(0)-catalyzed aminocarbonylation of aryl halides

WCl6 in dimethyl formamide (DMF) is introduced as a new reagent system for aminocarbonylation of aryl halides in the presence of PdCl2 as pre-catalyst without any phosphorous ligand. Aryl iodides, bromides as well as chlorides were efficiently converted to their corresponding N,N-dimethyl amides in good to high yields. In this protocol, WCl6/DMF is responsible for the generation of both Pd(0) catalyst as well as the formation of a Vilsmeier imminium type intermediate.