Quantum chemical study of the isomerization of 24-methylenecycloartanol, a potential marker of olive oil refining

Abstract

Quantum chemical calculations on the isomerization of 24-methylenecycloartanol are described. An energetically viable mechanism, with a rate-determining protonation step, is proposed. This rearrangement may find applicability in tests for determining if an olive oil has been refined.

The results of density functional calculations on the mechanism of a rearrangement of a sterol proposed to occur during olive oil heating are described. These results indicate that this rearrangement can indeed occur at a fast rate under refining conditions, but will not occur at an appreciable rate under conditions for producing extra virgin olive oil.

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Acknowledgments

We gratefully acknowledge support from the National Science Foundation (CHE-0957416 to DJT, a graduate research fellowship to HBW, and support through the XSEDE program). We also acknowledge T. Newman and G. Nepomuceno for their work on the development and implementation of AsteriX-BVI, and Dr. C. Hamann for valuable insight into IRC calculations.

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Correspondence to Dean J. Tantillo or Selina C. Wang.

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Supporting Information

Additional Supporting Information (details on computational approaches, along with coordinates and energies for computed structures and IRC data) may be found in the online version of this article. (PDF 3457 kb)

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Wedler, H.B., Pemberton, R.P., Lounnas, V. et al. Quantum chemical study of the isomerization of 24-methylenecycloartanol, a potential marker of olive oil refining. J Mol Model 21, 111 (2015). https://doi.org/10.1007/s00894-015-2652-y

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Keywords

  • Olive oil
  • Carbocation
  • Quantum chemistry
  • Mechanism