FeCl3‐Catalyzed Photochemical Reductive Transamidation of Nitroarenes: A Sustainable Approach Using Sacrificial C−H Bonds

Abstract A sustainable photochemical reductive transamidation of nitroarenes catalyzed by FeCl 3 under blue LED irradiation is reported. This method eliminates the need for pre‐reduction steps or stoichiometric reducing agents by utilizing sacrificial C−H bonds from organic solvents. The reaction proceeds via FeCl 3 ‐catalyzed single‐electron transfer (SET) and hydrogen atom transfer (HAT) cascades. A previously unreported intermediate formed between nitroarenes and N ‐methylpyrrolidone (NMP) is discovered, playing a crucial role in facilitating substitution with amides. The method exhibits broad functional group tolerance and achieves yields up to 82%, demonstrating compatibility with a wide range of nitroarenes and amides.