Amino Acids as Carboxyl Sources for the Palladium‐Catalyzed Remote Selective C(sp2)─H Acyloxylation

An efficient palladium‐catalyzed remote selective C(sp²)─H acyloxylation of arenes and alkenes, assisted by a thioether weak‐coordination directing group, has been developed. This acyloxylation protocol exhibits broad functional group tolerance and affords δ‐position‐selective products in up to 90% yield. Notably, a diverse range of substrates including amino acids, peptide derivatives, and carboxylic acid‐containing drugs is compatible under mild reaction conditions. Preliminary mechanistic studies suggest that an irreversible Pd(II)/Pd(IV) reaction model is likely involved in this process. The directing groups can be further transformed into synthetically useful functional groups or efficiently removed.