Carbonylation of C−N Bonds in Tertiary Amines Catalyzed by Low‐Valent Iron Catalysts

The first iron catalysts able to promote the formal insertion of CO into the C-N bond of amines are reported. Using low-valent iron complexes, including K2 [Fe(CO)4 ], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl3 and Nd(OTf)3 , have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).