DFT computational schemes for 1 H and 13 C NMR chemical shifts of natural products, exemplified by strychnine.

Abstract

A number of computational schemes based on different Density Functional Theory (DFT) functionals in combination with a number of basis sets were tested in the calculation of 1 H and 13 C NMR chemical shifts of strychnine, as a typical representative of the vitally important natural products, and used as a challenging benchmark and a rigorous test for such calculations. It was found that the most accurate computational scheme, as compared with experiment, was PBE0/pcSseg-4//pcseg-3 characterized by a mean absolute error of 0.07 ppm for the range of about 7 ppm for 1 H NMR chemical shifts and that of only 1.13 ppm for 13 C NMR chemical shifts spread over the range of about 150 ppm. For more practical purposes, including investigation of larger molecules from this series, a much more economical computational scheme, PBE0/pcSseg-2//pcseg-2, characterized by almost the same accuracy and much less computational demand, was recommended.