Absolute configuration of the ocimene monoterpenoids from Artemisia absinthium

Luis F. Julio, Eleuterio Burgueño-Tapia, Carmen E. Díaz, Nury Pérez-Hernández, Azucena González-Coloma, Pedro Joseph-Nathan

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

© 2017 Wiley Periodicals, Inc. The absolute configuration (AC) of the naturally occurring ocimenes (−)-(3S,5Z)-2,6-dimethyl-2,3-epoxyocta-5,7-diene (1) and (−)-(3S,5Z)-2,6-dimethylocta-5,7-dien-2,3-diol (2), isolated from the essential oils of domesticated specimens of Artemisia absinthium, followed by vibrational circular dichroism (VCD) studies of 1, as well as from the acetonide 3 and the monoacetate 4, both derived from 2, since secondary alcohols are not the best functional groups to be present during VCD studies in solution due to intermolecular associations. The AC follows from comparison of experimental and calculated VCD spectra that were obtained by Density Functional Theory computation at the B3LYP/DGDZVP level of theory. Careful nuclear magnetic resonance (NMR) measurements were compared with literature values, providing for the first time systematic 1H and 13C chemical shift data. Regarding homonuclear 1H coupling constants, after performing a few irradiation experiments that showed the presence of several small long-range interactions, the complete set of coupling constants for 3, which is representative of the four studied molecules, was determined by iterations using the PERCH software. This procedure even allowed assigning the pro-R and pro-S methyl group signals of the two gem-dimethyl groups present in 3.
Original languageAmerican English
Pages (from-to)716-725
Number of pages643
JournalChirality
DOIs
StatePublished - 1 Nov 2017

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Artemisia absinthium
Monoterpenes
Circular Dichroism
Magnetic resonance measurement
Gems
Essential oils
Chemical shift
Volatile Oils
Functional groups
Density functional theory
Alcohols
Magnetic Resonance Spectroscopy
Software
Nuclear magnetic resonance
Irradiation
Molecules
absinthium
Experiments

Cite this

Julio, L. F., Burgueño-Tapia, E., Díaz, C. E., Pérez-Hernández, N., González-Coloma, A., & Joseph-Nathan, P. (2017). Absolute configuration of the ocimene monoterpenoids from Artemisia absinthium. Chirality, 716-725. https://doi.org/10.1002/chir.22741
Julio, Luis F. ; Burgueño-Tapia, Eleuterio ; Díaz, Carmen E. ; Pérez-Hernández, Nury ; González-Coloma, Azucena ; Joseph-Nathan, Pedro. / Absolute configuration of the ocimene monoterpenoids from Artemisia absinthium. In: Chirality. 2017 ; pp. 716-725.
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Julio, LF, Burgueño-Tapia, E, Díaz, CE, Pérez-Hernández, N, González-Coloma, A & Joseph-Nathan, P 2017, 'Absolute configuration of the ocimene monoterpenoids from Artemisia absinthium', Chirality, pp. 716-725. https://doi.org/10.1002/chir.22741

Absolute configuration of the ocimene monoterpenoids from Artemisia absinthium. / Julio, Luis F.; Burgueño-Tapia, Eleuterio; Díaz, Carmen E.; Pérez-Hernández, Nury; González-Coloma, Azucena; Joseph-Nathan, Pedro.

In: Chirality, 01.11.2017, p. 716-725.

Research output: Contribution to journalArticle

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Julio LF, Burgueño-Tapia E, Díaz CE, Pérez-Hernández N, González-Coloma A, Joseph-Nathan P. Absolute configuration of the ocimene monoterpenoids from Artemisia absinthium. Chirality. 2017 Nov 1;716-725. https://doi.org/10.1002/chir.22741