A Route for the Total Synthesis of Enantiomerically Enriched Jasmonates 12‐COOH‐JA and 12‐COOH‐JA‐Ile

Heinrich, Clément F.; Widemann, Émilie; Sanz, Jérémie; Lugan, Raphaël; Heitz, Thierry; Pinot, Franck; Miesch, Michel; Miesch, Laurence

doi:10.1002/ejoc.201403347

Cited by 6 publications

(5 citation statements)

References 24 publications

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“…Long synthetic routes to these important metabolites are no longer needed. 41 Saponification of ( 9) afforded the free acid (10) quantitatively, which was employed in the next step without purification. Conjugation of L-Ile to (10) was carried out according to the procedure described for the linolenic acid/L-Ile conjugate.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis, structural characterization and biological activity of two diastereomeric JA-Ile macrolactones

et al. 2015

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Jasmonates are phytohormones involved in a wide range of plant processes, including growth, development, senescence, and defense. Jasmonoyl-L-isoleucine (JA-Ile, 2), an amino acid conjugate of jasmonic acid (JA, 1), has been identified as a bioactive endogenous jasmonate. However, JA-Ile (2) analogues trigger different responses in the plant. ω-Hydroxylation of the pentenyl side chain leads to the inactive 12-OH-JA-Ile (3) acting as a “stop” signal. On the other hand, a lactone derivative of 12-OH-JA (5) (jasmine ketolactone, JKL) occurs in nature, although with no known biological function. Inspired by the chemical structure of JKL (6) and in order to further explore the potential biological activities of 12-modified JA-Ile derivatives, we synthesized two macrolactones (JA-Ile-lactones (4a) and (4b)) derived from 12-OH-JA-Ile (3). The biological activity of (4a) and (4b) was tested for their ability to elicit nicotine production, a well-known jasmonate dependent secondary metabolite. Both macrolactones showed strong biological activity, inducing nicotine accumulation to a similar extent as methyl jasmonate does in Nicotiana attenuata leaves. Surprisingly, the highest nicotine contents were found in plants treated with the JA-Ile-lactone (4b), which has (3S,7S) configuration at the cyclopentanone not known from natural jasmonates. Macrolactone (4a) is a valuable standard to explore for its occurrence in nature.

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Section: Resultsmentioning

confidence: 99%

“…41 Saponification of (9) afforded the free acid (10) quantitatively, which was employed in the next step without purification. This is a reliable procedure to obtain 12-modified jasmonates enriched with the Z-isomer.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structural characterization and biological activity of two diastereomeric JA-Ile macrolactones

et al. 2015

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Section: Resultsmentioning

confidence: 99%

“…The HMBC cross-peak from H 2 -6″ ( δ H 4.07, 4.23) to C-9′′′′ ( δ C 166.1) indicated that the sinapoyl residue was linked to C-6″. As for aeswilflavonoside IC ( 3 ), a 5-[2-(carboxymethyl)-5-oxocyclopent-yl]pent-3-enoic acid 20 moiety was easily assembled by 1 H- 1 H COSY correlations between H-3′′′′ and H 2 -2′′′′, H-4′′′′; H-5′′′′ and H-4′′′′, H-1′′′′′; H-2′′′′′ and H-1′′′′′, H 2 -3′′′′′, H 2 -6′′′′′; H 2 -3′′′′′ and H 2 -4′′′′′, as well as the HMBC correlations from H-3′′′′ to C-1′′′′; H-1′′′′′, H-2′′′′′, H 2 -3′′′′′, H 2 -4′′′′′, H 2 -5′′′′ to C-5′′′′′; H-2′′′′′, H 2 -6′′′′′ to C-7′′′′′ ( Fig. 2 ).…”

Section: Resultsmentioning

confidence: 99%

NO Release Inhibitory Activity of Flavonoids from Aesculus Wilsonii Seeds through MAPK (P38), NF-κB, and STAT3 Cross-Talk Signaling Pathways

et al. 2022

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The flavonoid constituents of Aesculus wilsonii, a source of the Chinese medicinal drug Suo Luo Zi, and their in vitro anti-inflammatory effects were investigated. Fifteen flavonoids, including aeswilflavonosides IA–IC (1–3) and aeswilflavonosides IIA–IIE (4–8), along with seven known derivatives were isolated from a seed extract. Their structures were elucidated by extensive spectroscopic methods, acid and alkaline hydrolysis, and calculated electronic circular dichroism (ECD) spectra. Among them, compounds 3 and 7 possess a 5-[2-(carboxymethyl)-5-oxocyclopent-yl]pent-3-enylate or oleuropeoylate substituent, respectively, which are rarely reported in flavonoids. Compounds 2, 3, 7, and 1215 were found to inhibit lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW 264.7 cell lines. In a mechanistic assay, the flavonoid glycosides 2, 3, and 7 reduced the expressions of interleukin-6 (IL-6) and tumor necrosis factor (TNF-α) induced by LPS. Further investigations suggest that 2 and 3 down-regulate the protein expression of TNF-α and IL-6 by inhibiting the phosphorylation of p38. Compound 7 was found to reduce the production of inducible nitric oxide synthase (iNOS), and the secrection of TNF-α and IL-6 through inhibiting nuclear factor kappa-light-chain-enhancer of activated B (NF-κB) signaling pathway. Compounds 2, 3 and 7 possessed moderate inhibitory activity on the expression of signal transducer and activator of transcription 3 (STAT3). Taken together, the data indicate that the flavonoid glycosides of A. wilsonii seeds exhibit NO release inhibitory activity through mitogen-activated protein kinase (p38) [MAPK (p38)], NF-κB and STAT3 cross-talk signaling pathways.

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“…A synthetic supply of jasmonates is indispensable if their study is to be advanced 20 , 30 , 33 , 34 , and this work finally enables dn- cis / iso -OPDAs ( 4 and 5 ) and their potent catabolites ( 6 – 9 ) to be readily obtained. Our work is expected to accelerate biological studies of the signaling mechanisms of bryophyte hormones, which should lead to a better understanding of the evolutional origins of phytohormone signaling.…”

Section: Discussionmentioning

confidence: 99%

Syntheses of dinor-cis/iso-12-oxo-phytodienoic acid (dn-cis/iso-OPDAs), ancestral jasmonate phytohormones of the bryophyte Marchantia polymorpha L., and their catabolites

Wang

Sakurai

Kato

et al. 2021

Sci Rep

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In recent years, the biology of the evolutionary origin of phytohormone signaling has made significant progress. Among them, the ligand-receptor co-evolution found in jasmonate signaling has attracted the attention of plant scientists. Dinor-cis-12-oxo-phytodienoic acid (dn-cis-OPDA, 4) and dn-iso-OPDA (5) are ancestral plant hormones of the bryophyte Marchantia polymorpha L. We succeeded in the first practical synthetic supply of these hormones as well as their possible catabolites. These compounds are expected to be useful in the study of ancestral jasmonate signaling in bryophytes.

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A Route for the Total Synthesis of Enantiomerically Enriched Jasmonates 12‐COOH‐JA and 12‐COOH‐JA‐Ile

Cited by 6 publications

References 24 publications

Synthesis, structural characterization and biological activity of two diastereomeric JA-Ile macrolactones

Synthesis, structural characterization and biological activity of two diastereomeric JA-Ile macrolactones

NO Release Inhibitory Activity of Flavonoids from Aesculus Wilsonii Seeds through MAPK (P38), NF-κB, and STAT3 Cross-Talk Signaling Pathways

Syntheses of dinor-cis/iso-12-oxo-phytodienoic acid (dn-cis/iso-OPDAs), ancestral jasmonate phytohormones of the bryophyte Marchantia polymorpha L., and their catabolites

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