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Relative Configuration of Natural Products Using NMR Chemical Shifts

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Department of Chemistry, Quantum Theory Project, University of Florida, Gainesville, Florida 32611, Department of Biochemistry & Molecular Biology and McKnight Brain Institute, University of Florida, Gainesville, Florida 32610, Center for Medical, Agricultural and Veterinary Entomology, USDA-ARS, Gainesville, Florida 32604, and National High Magnetic Field Laboratory, University of Florida, Gainesville, Florida 32610
* Corresponding author. Phone: 352-392-6973. Fax: 352-392-8722. E-mail: [email protected]
†Department of Chemistry, Quantum Theory Project, University of Florida.
‡Department of Biochemistry & Molecular Biology and McKnight Brain Institute, University of Florida.
§Center for Medical, Agricultural and Veterinary Entomology, USDA-ARS.
⊥National High Magnetic Field Laboratory, University of Florida.
∥These authors contributed equally to this work.
Cite this: J. Nat. Prod. 2009, 72, 4, 709–713
Publication Date (Web):March 5, 2009
https://doi.org/10.1021/np8005056
Copyright © 2009 The American Chemical Society and American Society of Pharmacognosy

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    Abstract

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    We have measured and quantum chemically computed NMR chemical shifts for three monoterpene diastereomers produced by the walkingstick, Anisomorpha buprestoides. By taking into account the Boltzmann distribution of conformers, the combined RMSDs between experimental and calculated 1H and 13C NMR shifts were able to determine the correct isomer, especially when only aliphatic nuclei were used. The calculated relative energies and interproton distances were also consistent with chemical isomerization experiments and NOE-based interproton distance calculations. Complementary to the NOE-based method, a comparison between experimental and calculated NMR chemical shifts can provide an efficient method to assign the relative configuration of natural products.

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    Complete lists of experimental NOE distances and calculated distances, comparison plots of experimental NOE and theoretical distances, and the potential energy surface (PES) for molecules 14. This material is available free of charge via the Internet at http://pubs.acs.org.

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