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

Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 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.