A simple and general one-pot method was developed to give a-amino phosphonates from aldehydes + amines + dimethyl phosphite in LPDE. Optically active a-amino phosphonates were synthesized using (R)-(+), (S)-(-) alpha-methylbenzylamine, (R)-(-), (S)-(+) 2-phenylglycinol. (R)-(+) alpha-methylbenzylamine affords predominantly(S)-alpha-amino phosphonates and (R)-(-) 2-phenylglycinol leads predominantly to (R)-alpha-amino phosphonates. (C) 1998 Elsevier Science Ltd. All rights reserved.