5S, 8S-germacra-1E,6E-dien-5-ol from the oleoresin ofPicea ajanensis and its biomimetic cyclization

Ралдугин, В. А.; Salenko, V. L.; Gamov, N. S.; Titova, T. F.; Khan, V. A.; Pentegova, V. A.

doi:10.1007/bf00638775

Cited by 4 publications

(6 citation statements)

References 9 publications

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“…Allogermacranes, in which a trans , trans -cyclodeca-1,6-diene ring system is present, are not very abundant in nature and may play a different role in the biosynthesis of sesquiterpenes. Since the trans,trans- cyclodeca-1,6-diene unit is known to undergo a smooth photochemical [2 + 2] cycloaddition, allogermacranes are the most likely precursors of bourbonanes, a small class of sesquiterpenes possessing the cyclobuta[1,2:3,4]dicyclopentene skeleton 3 . In contrast to the synthesis of trans , trans -germacrane sesquiterpenes and their double bond stereoisomers, little attention has been paid to the synthesis of the regioisomeric allogermacranes …”

Section: Introductionmentioning

confidence: 99%

Relative and Absolute Configuration of Allohedycaryol. Enantiospecific Total Synthesis of Its Enantiomer

et al. 1996

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The enantiomer of (+)-allohedycaryol, a germacrane alcohol isolated from giant fennel (Ferula communis L.), has been synthesized, thereby elucidating the relative and absolute stereochemistry of the natural product. The synthesis of (-)-allohedycaryol started from (+)-alpha-cyperone (5) which was available in relatively large quantities via alkylation of imine 7 derived from (+)-dihydrocarvone and (R)-(+)-1-phenylethylamine. In a number of steps 5 was converted into the mesylate 4with a regio- and stereoselective epoxidation as the key step. A Marshall fragmentation of 4 was used to prepare the trans,trans-cyclodeca-1,6-diene ring present in allohedycaryol. The conformation of synthetic (-)-allohedycaryol was elucidated via photochemical conversion into a bourbonane system. The synthesis of (-)-allohedycaryol also showed that natural (+)-allohedycaryol has the opposite absolute stereochemistry to that normally found in higher plants.

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Section: Introductionmentioning

confidence: 99%

Relative and Absolute Configuration of Allohedycaryol. Enantiospecific Total Synthesis of Its Enantiomer

et al. 1996

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“…Identification of one or the other isomer has been performed using 1 H NMR data. For instance, a compound named 5 S ,8 S ‐germacra‐1 E ,6 E ‐dien‐5‐ol (synonym of germacra‐1(10),5‐dien‐4α‐ol) has been isolated from the oleoresin of Picea ajanensis . However, the relative stereochemistry of the asymmetric carbons is doubtful since it differs in the name and in the drawn chemical formula.…”

Section: Resultsmentioning

confidence: 99%

Germacra‐1(10),5‐dien‐4α‐ol in Fortunella sp. leaf oils

Sutour

Bradesi

Luro³

et al. 2015

Flavour & Fragrance J

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The composition of an oil sample isolated from leaves of Fortunella japonica (Thunb.) Swingle was investigated by combination of chromatographic and spectroscopic techniques. Among the compounds present at appreciable amounts, a special attention was brought to sesquiterpenes bearing a tertiary alcohol function and particularly to germacra-1(10),5-dien-4α-ol. Indeed, identification of diastereoisomers α and β of germacra-1(10),5-dien-4-ol has been the subject of controversy in the literature. We report here for the first time 13

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“…The acid-catalyzed, enforced chemical conversion of (À )-1 was previously reported, where the reaction conditions were far from physiological, giving a more complex reaction mixture. [18] In summary, the CS method enabled the conformational analysis of a flexible, oily compound, germacrene D-4-ol (1), by Xray crystallography. In addition, the CS method enabled the structure elucidation of 1-5 including their absolute stereochemistry based on the low value of the Flack parameter, although the Flack parameter is not fully decreased to zero.…”

mentioning

confidence: 99%

Conformational Analysis of (+)‐Germacrene D‐4‐ol Using the Crystalline Sponge Method to Elucidate the Origin of its Instability

Jung,

Mitsuhashi,

Kageyama

et al. 2024

Chemistry A European J

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Unsaturated cyclic terpenes often exhibit instability due to the proximation of C=C bonds in the cyclic skeleton, leading to nonenzymatic degradation. In this study, the crystalline sponge (CS) method was employed for the X‐ray conformational analysis of a minute amount of oily and cyclic terpene compound, (+)‐germacrene D‐4‐ol, which was produced by a terpene synthase OILTS under in vitro conditions. The CS method revealed a reactive conformation of the cyclic terpene with proximal double bonds. Under weakly acidic in vivo conditions, OILTS gave four pseudo‐natural products or artifacts. The CS method also elucidated the structures of these degraded compounds, proposing a degradation mechanism triggered by the transannular reactions.

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5S, 8S-germacra-1E,6E-dien-5-ol from the oleoresin ofPicea ajanensis and its biomimetic cyclization

Cited by 4 publications

References 9 publications

Relative and Absolute Configuration of Allohedycaryol. Enantiospecific Total Synthesis of Its Enantiomer

Relative and Absolute Configuration of Allohedycaryol. Enantiospecific Total Synthesis of Its Enantiomer

Germacra‐1(10),5‐dien‐4α‐ol in Fortunella sp. leaf oils

Conformational Analysis of (+)‐Germacrene D‐4‐ol Using the Crystalline Sponge Method to Elucidate the Origin of its Instability

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