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Conformational and electronic (AIM/NBO) study of unsubstituted A-type dimeric proanthocyanidin

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Abstract

The conformational space of the unsubstituted A-type dimeric proanthocyanidin was scanned using molecular dynamics at a semiempirical level, and complemented with functional density calculations. The lowest energy conformers were obtained. Electronic distributions were analysed at a higher calculation level, thus improving the basis set. A topological study based on Bader’s theory (AIM: atoms in molecules) and natural bond orbital (NBO) framework was performed. Furthermore, molecular electrostatic potential maps (MEPs) were obtained and analysed. NMR chemical shifts were calculated at ab initio level and further compared with previous experimental values; coupling constants were also calculated. The stereochemistry of the molecule is thoroughly discussed, revealing the key role that hyperconjugative interactions play in defining experimental trends. These results show the versatility of geminal spin–spin coupling 2J(C-1′,O) as a probe for stereochemical studies of proanthocyanidins.

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Acknowledgements

Thanks are due to CONICET, Universidad Nacional de La Plata and Universidad de Buenos Aires (Argentina) for financial support. One of us (A.B.P.) is a Senior Research Member of the National Research Council of Argentina (CONICET). A.H.J. is a Member of the Scientific Research Career (CIC, Provincia de Buenos Aires). R.M.L. acknowledges Universidad de la Cuenca del Plata (Corrientes, Argentina) for facilities provided during the course of this work.

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Authors and Affiliations

  1. Facultad de Ingeniería, Universidad de la Cuenca del Plata, Lavalle 50, 3400, Corrientes, Argentina

    Rosana M. Lobayan

  2. CEQUINOR Facultad de Ciencias Exactas y Facultad de Ingeniería, Universidad Nacional de La Plata, CC 962, 1900, La Plata, Argentina

    Alicia H. Jubert

  3. INIFTA (UNLP, CONICET), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 1900, La Plata, Argentina

    Martín G. Vitale

  4. PRALIB (UBA, CONICET), Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 956, C1113AAD, Buenos Aires, Argentina

    Alicia B. Pomilio

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  1. Rosana M. Lobayan
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  2. Alicia H. Jubert
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  4. Alicia B. Pomilio
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Correspondence to Rosana M. Lobayan.

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Lobayan, R.M., Jubert, A.H., Vitale, M.G. et al. Conformational and electronic (AIM/NBO) study of unsubstituted A-type dimeric proanthocyanidin. J Mol Model 15, 537–550 (2009). https://doi.org/10.1007/s00894-008-0389-6

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  • DOI: https://doi.org/10.1007/s00894-008-0389-6

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