Mn‐Catalyzed Selective Double and Mono‐N‐Formylation and N‐Methylation of Amines by using CO2

Abstract Functionalization of amines by using CO 2 is of fundamental importance considering the abundance of amines and CO 2 . In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO 2 utilization as a C 1 building block. This study represents the first example of selective catalytic double N ‐formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.