Geometry optimization and GIAO (gauge including atomic orbitals) 13C NMR chemical shift calculations at Hartree–Fock level, using the 6-31G(d) basis set, are proposed as a tool to be applied in the structural characterization of new organic compounds, thus providing useful support in the interpretation of experimental NMR data. Parameters related to linear correlation plots of computed versus experimental 13C NMR chemical shifts for fourteen low-polar natural products, containing 10–20 carbon atoms, were employed to assess the reliability of the proposed structures. A comparison with the hybrid B3LYP method was carried out to evaluate electron correlation contributions to the calculation of 13C NMR chemical shifts and, eventually, to extend the applicability of such computational methods to the interpretation of NMR spectra in apolar solutions. The method was tested by studying three examples of revised structure assignments, analyzing how the theoretical 13C chemical shifts of both correct and incorrect structures matched the experimental data.

Structure Validation of Natural products by Quantum-Mechanical GIAO Calculations of 13C NMR Chemical Shifts

RICCIO, Raffaele;BIFULCO, Giuseppe
2002

Abstract

Geometry optimization and GIAO (gauge including atomic orbitals) 13C NMR chemical shift calculations at Hartree–Fock level, using the 6-31G(d) basis set, are proposed as a tool to be applied in the structural characterization of new organic compounds, thus providing useful support in the interpretation of experimental NMR data. Parameters related to linear correlation plots of computed versus experimental 13C NMR chemical shifts for fourteen low-polar natural products, containing 10–20 carbon atoms, were employed to assess the reliability of the proposed structures. A comparison with the hybrid B3LYP method was carried out to evaluate electron correlation contributions to the calculation of 13C NMR chemical shifts and, eventually, to extend the applicability of such computational methods to the interpretation of NMR spectra in apolar solutions. The method was tested by studying three examples of revised structure assignments, analyzing how the theoretical 13C chemical shifts of both correct and incorrect structures matched the experimental data.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11386/1065917
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