The conformational dependence of vicinal 15N-C-C-H coupling constants in peptides

The conformational dependence of vicinal ¹⁵N-C-C-H coupling in N-methylacetamide as a model compound for coupling in the peptide backbone is investigated by means of the self-consistent perturbation formulation for coupling constants in the INDO approximation of self-consistent-field molecular orbital theory. Because the calculated coupling constants cover a range of at least 7 Hz, they should be useful in determining the ψ angles in peptides. The prediction of opposite signs for gauche and trans coupling indicates the need for sign determination. Non-negligible coupling constants of positive sign for the gauche arrangements are undoubtedly due to a substituent effect involving the lone pair electrons on the nitrogen and the π-electrons of the carbonyl group. Calculated results are compared with the available experimental data.