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Stereochemical analysis of (+)-limonene using theoretical and experimental NMR and chiroptical data.

MPS-Authors
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Reinscheid,  F.
Department of NMR Based Structural Biology, MPI for Biophysical Chemistry, Max Planck Society;

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Reinscheid,  U. M.
Department of NMR Based Structural Biology, MPI for Biophysical Chemistry, Max Planck Society;

Fulltext (public)

2242330.pdf
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Supplementary Material (public)

2242330_Suppl.doc
(Supplementary material), 3MB

Citation

Reinscheid, F., & Reinscheid, U. M. (2016). Stereochemical analysis of (+)-limonene using theoretical and experimental NMR and chiroptical data. Journal of Molecular Structure, 1106, 141-153. doi:10.1016/j.molstruc.2015.10.061.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0029-5AA7-3
Abstract
Using limonene as test molecule, the success and the limitations of three chiroptical methods (optical rotatory dispersion (ORD), electronic and vibrational circular dichroism, ECD and VCD) could be demonstrated. At quite low levels of theory (mpw1pw91/cc-pvdz, IEFPCM (integral equation formalism polarizable continuum model)) the experimental ORD values differ by less than 10 units from the calculated values. The modelling in the condensed phase still represents a challenge so that experimental NMR data were used to test for aggregation and solvent solute interactions. After establishing a reasonable structural model, only the ECD spectra prediction showed a decisive dependence on the basis set: only augmented (in the case of Dunning's basis sets) or diffuse (in the case of Pople's basis sets) basis sets predicted the position and shape of the ECD bands correctly. Based on these result we propose a procedure to assign the absolute configuration (AC) of an unknown compound using the comparison between experimental and calculated chiroptical data.