Commonly used DFT methods for the calculation of (1)J(CH) coupling constants have typically required the application of ad hoc correction factors, modification of functionals, or empirical scaling to improve the fit between predicted and experimental values. Here we demonstrate that highly accurate 1JCH coupling predictions can be obtained without such adjustments by careful selection of DFT methods for geometry optimization and J-coupling calculations (e.g. B3LYP/6-31G(d,p)(mixed)// mPW1PW/cc-pVTZ). The proposed method was cross-validated against a diverse set of 122 1JCH couplings and was successfully applied to the conformational and stereochemical analysis of strychnine and a previously unreported trachylobane diterpene natural product.
Enhancing the utility of 1: J CH coupling constants in structural studies through optimized DFT analysis
De Tommasi N.;Bifulco G.;
2019-01-01
Abstract
Commonly used DFT methods for the calculation of (1)J(CH) coupling constants have typically required the application of ad hoc correction factors, modification of functionals, or empirical scaling to improve the fit between predicted and experimental values. Here we demonstrate that highly accurate 1JCH coupling predictions can be obtained without such adjustments by careful selection of DFT methods for geometry optimization and J-coupling calculations (e.g. B3LYP/6-31G(d,p)(mixed)// mPW1PW/cc-pVTZ). The proposed method was cross-validated against a diverse set of 122 1JCH couplings and was successfully applied to the conformational and stereochemical analysis of strychnine and a previously unreported trachylobane diterpene natural product.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
