Determination of the Absolute Configuration of a Monoglyceride Antibolting Compound and Isolation of Related Compounds from Radish Leaves (<i>Raphanus sativus</i>)

Ogihara, Tsuyoshi; Amano, Naruki; Mitsui, Yuki; Fujino, Kazuo; Ohta, Hiroyuki; Takahashi, Kosaku; Matsuura, Hideyuki

doi:10.1021/acs.jnatprod.6b00746

Cited by 10 publications

(4 citation statements)

References 19 publications

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“…To elucidate the biosynthetic pathway to give 1, (9Z,12Z,15Z)-N-(2,3-dihydroxypropyl) octadeca-9,12,15-trienamide (7) and (8) were synthesized according to the reported methods (Scheme 2). 9,11 The conversion of amide analogue 7 to 8 was envisioned as a model case that would not interfere with endogenous metabolism. Furthermore, α-LA-α-monoglyceride-d 5 (9) and cis-OPDA-α-monoglyceride-d 5 (10), the deuterated analogue of 1, having five deuterium atoms on the glycerol moiety, were synthesized according to reported methods (Scheme 3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Furthermore, α-LA-α-monoglyceride-d 5 (9) and cis-OPDA-α-monoglyceride-d 5 (10), the deuterated analogue of 1, having five deuterium atoms on the glycerol moiety, were synthesized according to reported methods (Scheme 3). 11 Compounds 8 and 10 were used as authentic compounds for UPLC MS/MS analysis to check the existence of the compounds derived from plant material, and 7 and 9 were used to be exogenously applied to wounded leaves of A. thaliana. The leaves given wound stress were harvested, extracted, and partially purified, and a portion of the extract was subjected to UPLC MS/MS analysis in MRM positive mode, whose MS/MS chromatograms are given in Figures 6 and 7, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Isolation and Structure Determination of cis-OPDA-α-Monoglyceride from Arabidopsis thaliana

Hirota,

Ito,

Inoue

et al. 2024

J. Nat. Prod.

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cis-12-oxo-Phytodieneoic acid-α-monoglyceride (1) was isolated from Arabidopsis thaliana. The chemical structure of 1 was elucidated based on exhaustive 1D and 2D NMR spectroscopic measurements and supported by FDMS and HRFDMS data. The absolute configuration of the cis-OPDA moiety in 1 was determined by comparison of 1 H NMR spectra and ECD measurements. With respect to the absolute configuration of the β-position of the glycerol backbone, the 2:3 ratio of (S) to (R) was determined by making ester-bonded derivatives with (R)-(+)-α-methoxy-α-trifluoromethylphenylacetyl chloride and comparing 1 H NMR spectra. Wounding stress did not increase endogenous levels of 1, and it was revealed 1 had an inhibitory effect of A. thaliana post germination growth. Notably, the endogenous amount of 1 was higher than the amounts of (+)-7-iso-jasmonic acid and (+)-cis-OPDA in intact plants. 1 also showed antimicrobial activity against Gram-positive bacteria, but jasmonic acid did not. It was also found that α-linolenic acid-α-monoglyceride was converted into 1 in the A. thaliana plant, which implied α-linolenic acid-α-monoglyceride was a biosynthetic intermediate of 1.O xylipin is the general term for structurally diverse plant metabolites produced through oxidation steps of unsaturated fatty acids, including aldehydes, divinyl ethers, oxo, keto, hydroxy, and hydroperoxy derivatives. These molecules play a pivotal role in plants because they are essential for developmental processes and defense. 1 Among oxylipins, jasmonates are representative examples. The compounds are biosynthesized using (+)-cis-12-oxo-phytodienoic acid ((+)-cis-OPDA) or (+)-dinor-cis-OPDA as common intermediates, in which (+)-7-iso-jasmonic acid ((+)-7-iso-JA) is a representative biologically active compound that is easily epimerized into (−)-JA during the process of isolation. 2 α-Linolenic acid (α-LA) and (13Z, 10Z, 7Z)-hexadeca-13,10,7-trienoic acid (HA) released by the lipase enzyme are oxygenated by 13-and 11-lipoxygenase (13-/11-LOX) enzymes, respectively, to afford 13-and 11-hydroperoxide intermediates, which are then catabolized through coupled dehydration−cyclization reactions catalyzed by allene oxide synthase (AOS) and allene oxide cyclase (AOC) enzymes to give cyclopentenones, (+)-cis-OPDA and (+)-dinor-cis-OPDA.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Isolation and Structure Determination of cis-OPDA-α-Monoglyceride from Arabidopsis thaliana

Hirota,

Ito,

Inoue

et al. 2024

J. Nat. Prod.

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“…Repeated column chromatography for the n-BuOH Fr of M. verticillata aerial parts led to the isolation of four glycerides (1-4), which were identified as (2S)-1-O-palmitoyl glyceride [24], (2S)-1-O-stearoyl glyceride [25], (2S)-1-Olinolenoyl glyceride [26], and (2S)-1,2-di-O-linoleoyl glyceride [27], respectively, based on NMR, IR, FAB-MS, GC-MS, and FAB-MS analyses in addition to comparison of the data with those in literatures (Table 1).…”

Section: Resultsmentioning

confidence: 99%

Glycerides isolated from the aerial parts of Malva verticillata cause immunomodulation effects via splenocyte function and NK anti-tumor activity

Castañeda

Joo

et al. 2018

Food Sci Biotechnol

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A preliminary study revealed that a 10 µg/mL -BuOH fraction of aerial parts significantly enhanced splenocyte proliferation and induced significant enhancement of natural-killer (NK) cell activity against tumor cells (YAC-1). This study was initiated to identify the principal components that exhibited these activities, and four glycerides were isolated through repeated SiO and ODS column chromatography. Structures of compounds - were determined to be (2)-1--palmitoyl glyceride, (2)-1--stearoyl glyceride, (2)-1--linolenoyl glyceride, and (2)-1,2-di--linoleoyl glyceride, respectively. Compounds - showed potential immune-enhancing activity in murine splenocyte and natural-killer (NK) cells at 10 µM. In contrast, compound showed weak activity, indicating the monoacyl glycerides (-) are more effective than diacyl glyceride (). Also, the longer the carbon number of the fatty acid in monoacyl glyceride, the better the activity, and the monoacyl glyceride including an unsaturated fatty acid () is more effective than the glycerides including the saturated fatty acids (-).

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“…In the current work, it was obtained as a nearly racemic mixture (

0.3; c 0.10, MeOH) and was not separable on both normal-phase and reversed-phase chiral HPLC columns. The other known analogues were identified to be (9 Z ,12 Z ,14 E )-16-oxo-octadecatrienoic acid ( 11 ) [ 18 ], (10 Z ,12 E ,14 Z )-9,16-dioxo-octadecatrienoic acid ( 12 ) [ 19 ], linoleic acid ( 13 ) [ 20 ], β -(9′ Z ,12′ Z ,15′ Z )-octadecatrienoic acid monoglyceride ( 14 ) [ 21 ], 1- O -(9Z,12Z)-octadecadienoyl glycerol ( 15 ) [ 22 ], α -(9′ Z ,12′ Z ,15′ Z )-octadecatrienoic acid monoglyceride ( 16 ) [ 21 ], 1- O -(10 E ,12 E )-9-oxo-octadecadienoyl glycerol ( 17 ) [ 23 ], 1- O -(9 Z ,11 E )-13-oxo-octadecadienoyl glycerol ( 18 ) [ 24 ], and 1- O -(9 Z ,11 E )-9-oxo-octadecadienoyl glycerol ( 19 ) [ 24 ] by spectroscopic data.…”

Section: Resultsmentioning

confidence: 99%

New Octadecanoid Enantiomers from the Whole Plants of Plantago depressa

Song

Zhu

et al. 2018

Molecules

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In this study, 19 octadecanoid derivatives—four pairs of enantiomers (1–8), two racemic/scalemic mixtures (9–10), and nine biosynthetically related analogues—were obtained from the ethanolic extract of a Chinese medicinal plant, Plantago depressa Willd. Their structures were elucidated on the basis of detailed spectroscopic analyses, with the absolute configurations of the new compounds assigned by time-dependent density functional theory (TD-DFT)-based electronic circular dichroism (ECD) calculations. Six of them (1, 3–6, and 9) were reported for the first time, while 2, 7, and 8 have been previously described as derivatives and are currently obtained as natural products. Our bioassays have established that selective compounds show in vitro anti-inflammatory activity by inhibiting lipopolysaccharide-induced nitric oxide (NO) production in mouse macrophage RAW 264.7 cells.

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Determination of the Absolute Configuration of a Monoglyceride Antibolting Compound and Isolation of Related Compounds from Radish Leaves (Raphanus sativus)

Cited by 10 publications

References 19 publications

Isolation and Structure Determination of cis-OPDA-α-Monoglyceride from Arabidopsis thaliana

Isolation and Structure Determination of cis-OPDA-α-Monoglyceride from Arabidopsis thaliana

Glycerides isolated from the aerial parts of Malva verticillata cause immunomodulation effects via splenocyte function and NK anti-tumor activity

New Octadecanoid Enantiomers from the Whole Plants of Plantago depressa

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