Direct Synthesis of -Aminophosphonates from Amines, Alcohols, and White Phosphorus

Developing practical strategies for the synthesis of organophosphorus compounds (OPCs) from white phosphorus (P4) without the use of Cl2 and PCl3 remains a significant challenge. The first multicom-ponent oxidative alpha-phosphonylation of amines with P4 and alcohols has been developed. With the use of copper(II) as the catalyst and air as the safe oxidant, structurally sophisticated alpha-aminophosphonates have been prepared in high yields. Furthermore, this method is also suitable for selective construction of P-O-P compounds. The reaction is characterized by a complete conversion of P4. The activation of P4 with transition metals often leads to formation of complexes [MxPy]n associated with the deactivation of transition metals. This breakthrough showcases the potential of transition-metal-catalyzed reactions in elemental phosphorus chemistry. Direct conversion of P4 into pyrophosphates ROH 1/4 P P P P CuCl2 (cat), TMEDA, air, 70 degrees C Pyrophosphates O O (RO)2P O P(OR)2 5 examples NR1 N R1 ROH Cu(OAc)2 (cat), air, 70 degrees C Phosphonylation of sp3 carbon atoms with P4 OR P O OR Cl2- and PCl3- free 35 examples