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

We have developed a palladium-catalyzed remote selective C(sp ²)─H acyloxylation reaction using amino acids as carboxyl sources. This method efficiently delivers a series of amino acid-substituted aryl (alkenyl) ester derivatives in good to high yields.

Abstract

An efficient palladium-catalyzed remote selective C(sp ²)─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.

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