A metal-free synthesis of phosphoramidates via I-catalyzed oxidative coupling of anilines/amines with H-phosphonates.

An efficient and environmentally benign protocol for synthesizing valuable and structurally diverse phosphoramidates via the sodium iodide (NaI)-catalyzed oxidative cross-coupling of various H-phosphonates with both aromatic and aliphatic amines. This new method utilizes HO (30% aq.) as a green oxidant, ethyl acetate (EA) as a renewable, low-toxic solvent, and inexpensive, readily available NaI (10 mol%) as the sole catalyst, circumventing the need for toxic reagents, transition metal catalysts, and special equipment. It exhibits excellent compatibility with a wide range of aromatic and aliphatic amines, as well as several amino-containing pharmaceuticals, including Vortioxetine, Fluoxetine, Ceritinib, Linagliptin, and Crizotinib.