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.

A direct phosphorylation of the sp3C–CN bond catalyzed by a nickel catalyst is disclosed. A wide range of primary nitriles readily coupled with secondary phosphine oxides to produce the corresponding phosphorylated products in high yields. As a key step, this new method was applied to the synthesis of anticancer drug Combretastatin-A4, significantly shortening its synthetic path.

A silver-free palladium-catalyzed dehydrogenative phosphorylation of terminal alkynes with hydrogen phosphine oxides has been developed. Both aromatic and aliphatic terminal alkynes including those bearing functional groups coupled readily with hydrogen phosphine oxides, producing the corresponding value-added alkynylphosphine oxides in good to excellent yields. This reaction could be easily conducted at gram scales (10 mmol) without any decrease of the reaction efficiency, showing highly potential synthetic value in organic synthesis. A plausible Pd(0)/Pd(II) mechanism is proposed.

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