Dimethylphosphinylmethylamine (1) and its aldimines 2 were used for the preparation of dimethyl and diethyl α-amino(aryl)methylphosphonates 3a - l via imine hydrophosphonylation and Kabachnik-Fields reaction. Their acid hydrolysis gave rise to the corresponding α-aminophosphonic acids 4a - e. Compounds 3 and 4 have two different phosphorus-containing groups - phosphonyl and dimethylphosphinyl - and might have interesting biological activity.