Iron‐Catalyzed Selective N‐Methylation and N‐Formylation of Amines with CO2

We herein describe an efficient iron‐catalyzed selective N‐methylation and N‐formylation of amines with CO2 and silane using mono‐phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe‐catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe‐catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late‐stage methylation and formylation of drug molecules containing amine moiety.