Highly Efficient Ruthenium‐Catalyzed N‐Formylation of Amines with H2 and CO2

Abstract A highly efficient catalyst system based on ruthenium‐pincer‐type complexes has been discovered for N‐formylation of various amines with CO 2 and H 2 , thus affording the corresponding formamides with excellent productivity (turnover numbers of up to 1 940 000 in a single batch) and selectivity. Using a simple catalyst recycling protocol, the catalyst was reused for 12 runs in N , N ‐dimethylformamide production without significant loss of activity, thus demonstrating the potential for practical utilization of this cost‐effective process. A one‐pot two‐step procedure for hydrogenation of CO 2 to methanol via the intermediacy of formamide formation has also been developed.