Résumé : 13C and 31P chemical shift data for eight 2-methoxy-1,3,2-dioxaphosphorinanes are reported. Examination of pairs of geometrical isomers, which differ only in the orientation of the OMe substituent on PIII, have shown that both the 31P and the 13C signals of C4,6 atoms appear 3-4 ppm at higher field when the OMe is axial compared with the equatorial isomer. This observation can be associated with the 1-3 syn diaxial interaction between the phosphorus axial substituent and the axial hydrogens on C4,6 and should thus constitute, in the future, a supplementary tool for the structural analysis of this kind of compound. Important long range δ effects were observed both on 13C and especially on 31P chemical shifts. It is suggested that the high field δe effects could reflect a direct stereoelectronic interaction between the P atom and the cyclic C-5 atom. This interpretation is supported by a study of the 31P...13C coupling constants and their stereochemical dependence. © 1973.