Mechanochemical Synthesis of Phosphoryl Amides and Esters from Diphenylphosphoryl Azides Under Mild Conditions

A simple, efficient, and one-step synthetic procedure to construct phosphoryl amides and esters has been developed applying mechanochemistry. A ball-milling technique easily facilitated the amination and esterification of diphenylphosphoryl azides (DPPA) in the presence of molecular iodine and sodium carbonate via cleavage of P—N bond. The metal-free mechanochemical protocol enables the transformations to provide a variety of alkyl phosphoryl amides and esters under solvent-free conditions and at room temperature. Moreover, readily available and inexpensive starting materials, excellent functional group compatibility, rapid synthesis, high yields of the products, and mild conditions are the notable features of the present method.