Tungstate-Catalyzed Bioinspired Decarboxylative Halogenation of Electron-Deficient (Hetero)Phenolic Acids

Phenolic acids (PAs) can be derived from lignin, and their value-added transformations provide a good renewable source for arenes. The halogenase-catalyzed decarboxylative halogenation of PAs is a key step in the biosynthesis of many halogenated natural products. Inspired by halogenase, herein we present a synthetically useful tungstate-catalyzed decarboxylative halogenation of electron-deficient (hetero)phenolic acids under mild conditions, based on which the antibiotic bromophene and its analogues were prepared concisely. Mechanism studies support the halogenation-decarboxylation procedure, but the decarboxylation-halogenation pathway cannot be excluded. Additionally, the chloride can reverse the selectivity between bromination and iodination in this reaction, somehow providing a useful perspective for the halide selectivity in vanadiumdependent haloperoxidase in seawater.