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). No pressure: Low‐valent iron complexes, such as K2[Fe(CO)4], efficiently catalyze the carbonylation of C−N bonds in amines by CO insertion. Lewis acids such as AlCl3 and Nd(OTf)3 have a positive influence on the catalytic activity and enable the carbonylation at a low pressure of CO.