Synthesis of α-aminophosphonates from α-hydroxyphosphonates; a theoretical study

Two types of reactions, namely the Pudovik reaction of benzaldehyde and acetophenone with diethyl phosphite as well as the substitution of the alpha-hydroxyphosphonates so-formed by primary amines to afford alpha-aminophosphonates, were evaluated by quantum chemical calculations at the B3LYP/6--31G(d,p) level. An unexpected neighboring group effect was found to enhance the substitution. A series of new alpha-aminophosphonates was synthesized by the microwave-assisted substitution of alpha-hydroxyphosphonates by alkylamines.