Efficient Pd‐Catalyzed Dehydrogenative Coupling of P(O)H with RSH: A Precise Construction of P(O)—S Bonds.

A Pd-catalyzed dehydrogenative phosphorylation of thiols is developed. A variety of thiols dehydrogenatively couple readily with all three kinds of P(O)–H compounds, i.e., H-phosphonates, H-phosphinates, and secondary phosphine oxides, providing a general access to the valuable phosphorothioates including the P-chiral compounds. A plausible mechanism is proposed.