Enhancing Ligand‐Free Fe‐Catalyzed Aminocarbonylation of Alkynes by ZrF4

Abstract Zirconium fluoride was utilized to promote efficiently iron‐catalyzed aminocarbonylation between alkynes and amines without the use of extra ligands. In particular, this new system is applicable to a wide range of amine and alkyne substrates affording α , β ‐unsaturated amides in good to excellent yields. Preliminary mechanistic studies reveal the activation model involving interactions of ZF 4 with both iron catalyst and amine substrates.