SbCl3 adsorbed on Al2O3 is found to be an efficient and recyclable catalyst in promoting three-component coupling reactions of aldehydes (aromatic and aliphatic), amines (aryl amines, aliphatic amines and esters of S-cc-amino acids) and dialkylphosphites to afford the corresponding alpha-aminophosphonates in high yields. The ethyl ester of S-phenylalanine was observed to yield the corresponding ot-aminophosphonate with S,S-diastereoisomer formed in dominance over the S,R-diastereoisomer. (C) 2008 Elsevier Ltd. All rights reserved.