Direct Decarboxylative Iodination and Chlorination of Alkyl Carboxylic Acids Enabled by Phosphine–Photoredox Catalysis

A phosphine–photoredox dual catalytic system enables efficient decarboxylative iodination and chlorination of alkyl carboxylic acids through in situ generation of N ‐hydroxyphthalimide (NHPI) ester intermediates, enabling broad substrate scope with high functional group tolerance under mild conditions. Utilizing ICH 2 CH 2 I as the iodine source, primary, secondary, and tertiary alkyl acids are converted to alkyl iodides, while selective chlorination of primary substrates is accomplished with DCE, demonstrating tunable halogenation reactivity. The versatility of this newly developed reaction is illustrated through its application in the late‐stage functionalization of complex natural products and pharmaceuticals.