Palladium‐Catalyzed Direct Decarbonylative Phosphorylation of Benzoic Acids with P(O)–H Compounds

A direct decarbonylative phosphorylation of benzoic acids catalyzed by palladium was disclosed. Under the reaction conditions, a wide range of benzoic acids coupled readily with all the three kinds of P(O)–H compounds, i.e. secondary phosphine oxides, H‐phosphinates and H‐phosphonates, producing the corresponding organophosphorus compounds in good to high yields. This reaction could be conducted at a gram scale and applied in the late‐stage phosphorylative modification of carboxylic acids drug molecules. These results well demonstrated the potential synthetic value of this new reaction in organic synthesis.