Stereochemical analysis of (+)-limonene using theoretical and experimental NMR and chiroptical data
作者： F. Reinscheid , U.M. Reinscheid
DOI: 10.1016/J.MOLSTRUC.2015.10.061
关键词: Absolute configuration 、 Chemistry 、 Polarizable continuum model 、 Thermodynamics 、 Vibrational circular dichroism 、 Spectral line 、 Computational chemistry 、 Optical rotatory dispersion 、 Molecule 、 Integral equation 、 Basis set
摘要: Abstract Using limonene as test molecule, the success and limitations of three chiroptical methods (optical rotatory dispersion (ORD), electronic vibrational circular dichroism, ECD VCD) could be demonstrated. At quite low levels theory (mpw1pw91/cc-pvdz, IEFPCM (integral equation formalism polarizable continuum model)) experimental ORD values differ by less than 10 units from calculated values. The modelling in condensed phase still represents a challenge so that NMR data were used to for aggregation solvent–solute interactions. After establishing reasonable structural model, only spectra prediction showed decisive dependence on basis set: augmented (in case Dunning's sets) or diffuse Pople's sets predicted position shape bands correctly. Based these result we propose procedure assign absolute configuration (AC) an unknown compound using comparison between data.
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