This work presents a photo‐redox vicinal dichlorination of acrylamides using a naturally abundant chlorine source (FeCl3). The LMCT of FeCl3 is responsible for the chlorine radical inducement, while the tetra‐n‐butylammonium decatungstate (TBADT) catalytic system enhanced the process. This method exhibits extraordinarily mild conditions, not requiring external ligands and low E factors, which enables scalable synthesis.
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