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A MnI catalyst featuring redox‐active tridentate phenalenyl (PLY) ligand has been used for catalytic N‐formylation of secondary amides and lactams under 1 atm CO2 as a C1 source at room temperature for the first time. The protocol is applicable to a wide range of secondary amides including heterocycles, bio‐active cinnamide derivatives and the diversification of therapeutic molecules. In‐depth mechanistic...
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