69. Palladium-Catalyzed Regioselective B(3,4)–H Acyloxylation of o-Carboranes

Fu, Y.; Li, Y.; Luo, D.; Lu, Y.; Huang, J.; Yang, Z.; Lu, J.; Jiang, Y.-Y.;* Lu, J.-Y.* Inorg. Chem. 2022, 61, 911–922. Download Link

Abstract: We disclose herein an efficient regioselective B(3,4)−H activation via a ligand strategy, affording B(3)- monoacyloxylated and B(3,4)-diacyloxylated o-carboranes. The identification of amino acid and phosphoric acid ligands is crucial for the success of B(3)-mono- and B(3,4)-diacyloxylation, respectively. This ligand approach is compatible with a broad range of carboxylic acids. The functionalization of complex drug molecules is demonstrated. Other acyloxyl sources, including sodium benzoate, benzoic anhydride, and iodobenzene diacetate, are also tolerated.