Abstract The intramolecular version of nucleophilic additon of phosphites to imines was carried out for the first time taking as an example β-aldiminoalkylphosphites, formed from chlorophosphites and β-aldiminoalcohols [N-(benzylidene)-2-aminoethanol and R-(+)-N- (benzylidene)-2-aminobutanol-1]. In these reactions, stereoisomeric 1, 4, 2- oxazaphosphorines were obtained in good yields. R-(+)-N-(benzylidene)-2-aminobutanol- ...