Mechanically Assisted PO, PN, and PS Bonds Formation

We report a general and efficient mechanochemical protocol for the formation of PO, PN, and PS bonds through the reaction of phosphoryl chlorides with O‐, N‐, and S‐centered nucleophiles. The transformation proceeds under solvent‐free conditions using ball milling in the presence of triethylamine and an inert grinding auxiliary, under ambient atmosphere and short reaction times. A broad range of primary and secondary alcohols, phenols, amines, anilines, and thiols are compatible with the methodology, affording the corresponding phosphates, phosphoramidates, and thiophosphates in moderate‐to‐excellent yields.