Vibrational Circular Dichroism Absolute Configuration Determination of Natural Products

Joseph‐Nathan, Pedro; Gordillo-Román, Bárbara

doi:10.1007/978-3-319-05275-5_4

Cited by 61 publications

(72 citation statements)

References 287 publications

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“…Comparison between the averaged calculated trans ‐chrysanthenyl acetate spectra and the experimental one is very poor (see Supporting Information). It can be concluded that (−)‐ cis ‐chrysanthenyl acetate is [(1 S ,5 R ,6 S )‐(−)‐2,7,7‐trimethylbicyclo[3.1.1]hept‐2‐en‐6‐yl acetate], in agreement with the previous assignment …”

Section: Resultssupporting

confidence: 91%

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Isolation of the major chiral compounds from Bubonium graveolens essential oil by HPLC and absolute configuration determination by VCD

et al. 2016

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The chirality issues in the essential oils (EOs) of leaves and flowers from Bubonium graveolens were addressed by chiral high-performance liquid chromatography (HPLC) with polarimetric detection and vibrational circular dichroism (VCD). The chemical compositions of the crude oils of three samples were established by gas chromatography / mass spectrometry (GC/MS). The well-known cis-chrysanthenyl acetate (1), oxocyclonerolidol (2), and the recently disclosed cis-acetyloxychrysanthenyl acetate (3), the three major chiral compounds, were isolated by preparative HPLC. The naturally occurring oxocycloneroledol (2), mostly found in the leaf oil (49.4-55.6%), presents a (+) sign in the mobile phase during HPLC on a chiral stationary phase (CSP) with a Jasco polarimetric detection. The naturally occurring cis-chrysanthenyl acetate (1) and cis-acetyloxychrysanthenyl acetate (3), mostly found in the flower EO (35.9-74.9% and 10.0-34.3%, respectively), both present a (-) sign. HPLC on a CSP with polarimetric detection is an unprecedented approach to readily differentiate the flower and leaf EOs according to their chiral signature. The comparison of the experimental and calculated VCD spectra of pure isolated 1, 2, and 3 provided their absolute configuration as being (1S,5R,6S)-(-)-2,7,7-trimethylbicyclo[3.1.1]hept-2-en-6-yl acetate 1, (2R,6R)-(+)-6-ethenyl-2,6-dimethyl-2-(4-methylpent-3-en-1-yl)dihydro-2H-pyran-3(4H)-one) 2 and (1S,5R,6R,7S)-(-)-7-(acetyloxy)-2,6-dimethylbicyclo[3.1.1]hept-2-en-6-yl]methyl acetate 3. Compounds 1, 2, and 3 were already known in B. graveolens but this is the first report of the absolute configuration of (+)-2 and (-)-3. The VCD chiral signatures of the crude oils were also recorded.

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Section: Resultssupporting

confidence: 91%

“…The absolute configuration of (−)‐ cis ‐chrysanthenyl acetate 1 [(1 S ,5 R ,6 S )‐(−)‐2,7,7‐trimethylbicyclo[3.1.1]hept‐2‐en‐6‐yl acetate] was established in the 1970s by a chemical correlation method on a sample isolated from Centipeda cunninghamii EO …”

Section: Resultsmentioning

confidence: 99%

Isolation of the major chiral compounds from Bubonium graveolens essential oil by HPLC and absolute configuration determination by VCD

et al. 2016

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“…Because the B3PW91 functional has been used successfully to compute the IR and VCD spectra of a great number of diterpenoids, 13 the quantum mechanics (QM) geometry optimization for the conformers was performed at the B3PW91/DGDZVP level of theory. A single conformer represented more than 99% of the conformational population of 3 and 4 .…”

Section: Resultsmentioning

confidence: 99%

Stereochemistry of a Second Riolozane and Other Diterpenoids from Jatropha dioica

et al. 2017

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The dichloromethane extract of the roots of Jatropha dioica afforded riolozatrione (1) and a C-6 epimer of riolozatrione, 6-epi-riolozatrione (2), as a new structure and only the second reported riolozane diterpenoid. The two known diterpenoids jatrophatrione (3) and citlalitrione (4) were also isolated and characterized. Both epimers 1 and 2 are genuine plant constituents, with 2 likely being the biosynthesis precursor of 1 due to the tendency for the quantitative transformation of 2 into 1 under base catalysis. The structural characterization and distinction of the stereoisomers utilized 1H iterative full-spin analysis, yielding complete J-correlation maps that were represented as quantum interaction and linkage tables. The absolute configuration of compounds 1–4 was established by means of vibrational circular dichroism and via X-ray diffraction analysis for 1, 2, and 4. Additionally, the cytotoxic and antiherpetic in vitro activities of the isolates were evaluated.

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“…The above calculations were done arbitrarily choosing the ( R ) absolute configuration (AC) for the sole stereogenic center of 1 and 2 , and therefore their AC determination turned out to be mandatory due to the reported optical activity data . VCD measurements were chosen due to their success for the AC determination of organic compounds, including natural products …”

Section: Resultsmentioning

confidence: 99%

Conformational, configurational, and supramolecular studies of podocephalol acetate from Lasianthaea aurea

et al. 2019

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Although podocephalol (1) and its derived acetate 2 were found in Lasianthaea podocephala four decades ago, and 1 was later detected in the essential oils of several vegetal species, its absolute configuration (AC) and conformational preferences remained to be established. The structures of ar‐himachalene 1, now isolated from Lasianthaea aurea, and its derived acetate 2, were herein confirmed by extensive 1D and 2D nuclear magnetic resonance (NMR) studies, while the conformational preferences of the cycloheptene was established by density functional theory (DFT) calculations, which in combination with vibrational circular dichroism measurements provided the (R) absolute configuration of the molecules. The structure and AC were further verified through the Flack and Hooft parameters calculations derived from single crystal X‐ray diffraction data of 2. In addition, careful evaluation of the crystal data allowed observing supramolecular layers cell package, an uncommon property in natural terpenes that might have potential applications. A transmission electron microscopy analysis of crystal of 2 was also possible, providing its physical characteristics at the micrometric scale.

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Vibrational Circular Dichroism Absolute Configuration Determination of Natural Products

Cited by 61 publications

References 287 publications

Isolation of the major chiral compounds from Bubonium graveolens essential oil by HPLC and absolute configuration determination by VCD

Isolation of the major chiral compounds from Bubonium graveolens essential oil by HPLC and absolute configuration determination by VCD

Stereochemistry of a Second Riolozane and Other Diterpenoids from Jatropha dioica

Conformational, configurational, and supramolecular studies of podocephalol acetate from Lasianthaea aurea

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