New α-aminophosphonates of the type (OCH2CMe2CH2O) P (O) CH (NHCO2R)(R′)[,, and] have been synthesized in high yields by a three-component reaction using (OCH2CMe2CH2O) PCl (), benzamide (or urethane or benzyl carbamate), and an aldehyde without using any catalyst under solvent-free conditions. This route can be readily adapted for bis-aminophosphonates as well as optically active binaphthoxy α-aminophosphonates; ...