85551-10-6Relevant academic research and scientific papers
Biosynthesis of Jasmonates from Linoleic Acid by the Fungus Fusarium oxysporum. Evidence for a Novel Allene Oxide Cyclase
Oliw, Ernst H.,Hamberg, Mats
, p. 543 - 556 (2019/08/12)
Fusarium oxysporum f. sp. tulipae (FOT) secretes (+)-7-iso-jasmonoyl-(S)-isoleucine ((+)-JA-Ile) to the growth medium together with about 10 times less 9,10-dihydro-(+)-7-iso-JA-Ile. Plants and fungi form (+)-JA-Ile from 18:3n-3 via 12-oxophytodienoic acid (12-OPDA), which is formed sequentially by 13S-lipoxygenase, allene oxide synthase (AOS), and allene oxide cyclase (AOC). Plant AOC does not accept linoleic acid (18:2n-6)-derived allene oxides and dihydrojasmonates are not commonly found in plants. This raises the question whether 18:2n-6 serves as the precursor of 9,10-dihydro-JA-Ile in Fusarium, or whether the latter arises by a putative reductase activity operating on the n-3 double bond of (+)-JA-Ile or one of its precursors. Incubation of pentadeuterated (d5) 18:3n-3 with mycelia led to the formation of d5-(+)-JA-Ile whereas d5-9,10-dihydro-JA-Ile was not detectable. In contrast, d5-9,10-dihydro-(+)-JA-Ile was produced following incubation of [17,17,18,18,18-2H5]linoleic acid (d5-18:2n-6). Furthermore, 9(S),13(S)-12-oxophytoenoic acid, the 15,16-dihydro analog of 12-OPDA, was formed upon incubation of unlabeled or d5-18:2n-6. Appearance of the α-ketol, 12-oxo-13-hydroxy-9-octadecenoic acid following incubation of unlabeled or [13C18]-labeled 13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid confirmed the involvement of AOS and the biosynthesis of the allene oxide 12,13(S)-epoxy-9,11-octadecadienoic acid. The lack of conversion of this allene oxide by AOC in higher plants necessitates the conclusion that the fungal AOC is distinct from the corresponding plant enzyme.
One-pot synthesis of bioactive cyclopentenones from α-linolenic acid and docosahexaenoic acid
Maynard, Daniel,Müller, Sara Mareike,Hahmeier, Monika,L?we, Jana,Feussner, Ivo,Gr?ger, Harald,Viehhauser, Andrea,Dietz, Karl-Josef
, p. 1356 - 1364 (2018/04/05)
Oxidation products of the poly-unsaturated fatty acids (PUFAs) arachidonic acid, α-linolenic acid and docosahexaenoic acid are bioactive in plants and animals as shown for the cyclopentenones prostaglandin 15d-PGJ2 and PGA2, cis-(+)-12-oxophytodienoic acid (12-OPDA), and 14-A-4 neuroprostane. In this study an inexpensive and simple enzymatic multi-step one-pot synthesis is presented for 12-OPDA, which is derived from α-linolenic acid, and the analogous docosahexaenoic acid (DHA)-derived cyclopentenone [(4Z,7Z,10Z)-12-[[-(1S,5S)-4-oxo-5-(2Z)-pent-2-en-1yl]-cyclopent-2-en-1yl] dodeca-4,7,10-trienoic acid, OCPD]. The three enzymes utilized in this multi-step cascade were crude soybean lipoxygenase or a recombinant lipoxygenase, allene oxide synthase and allene oxide cyclase from Arabidopsis thaliana. The DHA-derived 12-OPDA analog OCPD is predicted to have medicinal potential and signaling properties in planta. With OCPD in hand, it is shown that this compound interacts with chloroplast cyclophilin 20-3 and can be metabolized by 12-oxophytodienoic acid reductase (OPR3) which is an enzyme relevant for substrate bioactivity modulation in planta.
A lipoxygenase-divinyl ether synthase pathway in flax (Linum usitatissimum L.) leaves
Chechetkin, Ivan R.,Blufard, Alexander,Hamberg, Mats,Grechkin, Alexander N.
, p. 2008 - 2015 (2008/12/21)
Incubation of linoleic acid with an enzyme preparation from leaves of flax (Linum usitatissimum L.) led to the formation of a divinyl ether fatty acid, i.e. (9Z,11E,1′Z)-12-(1′-hexenyloxy)-9,11-dodecadienoic [(ω5Z)-etheroleic] acid, as well as smaller amounts of 13-hydroxy-9(Z),11(E)-octadecadienoic acid. The 13-hydroperoxide of linoleic acid afforded the same set of products, whereas incubations of α-linolenic acid and its 13-hydroperoxide afforded the divinyl ether (9Z,11E,1′Z,3′Z)-12-(1′,3′-hexadienyloxy)-9,11-dodecadienoic [(ω5Z)-etherolenic] as the main product. Identification of both divinyl ethers was substantiated by their UV, mass-, 1H NMR and COSY spectral data. In addition to the 13-lipoxygenase and divinyl ether synthase activities demonstrated by these results, flax leaves also contained allene oxide synthase activity as judged by the presence of endogenously formed (15Z)-cis-12-oxo-10,15-phytodienoic acid in all incubations.
Efficient total synthesis of 12-oxo-PDA and OPC-8:0
Ainai, Takayuki,Matsuumi, Michitaka,Kobayashi, Yuichi
, p. 7825 - 7832 (2007/10/03)
Although the supply of 12-oxo-PDA (1) and OPC-8:0 (2), the metabolites in the linolenic acid cascade leading to epi-jasmonic acid, is in demand for biological investigations, the previous syntheses of these metabolites suffer from low efficiency. Recently, we established a reaction to install an alkyl group onto the ring of cyclopentene monoacetate 4 by using a reagent system consisting of RMgCl (3 equiv) and CuCN (cat). The reaction was applied to ClMg(CH2)8OTBDPS (11) with modification by which the quantity of 11 could be reduced to 2 equiv without decreasing efficiency. The product 12 obtained in 88% yield with 92% regioselectivity was successfully transformed into the key iodolactone 17 in good yield, from which 12-oxo-PDA (1) and OPC-8:0 (2) were synthesized as described in Schemes 3 and 5 through construction of the cis side chain by Wittig reaction. Note that the Wittig reaction proceeded with high cis selectivity of > 95%, which is higher than in similar cases reported previously. Synthesis of the 13-isomers of 1 and 2 was also accomplished. With these compounds in hand, the epimerization speed of 1 and 2 was investigated to rule out overestimation of the finding in the literature that 1 and 2 change to the 13-epimers easily. Instead, we observed that the compounds are quite stable at room temperature for an extended period of days under slightly acidic and neutral conditions.
A new synthesis route to enantiomerically pure jasmonoids
Ernst, Martin,Helmchen, Guenter
, p. 4054 - 4056 (2007/10/03)
An important class of phytohormones are jasmonoids. A variety of jasmonoids in the natural cis configuration are now accessible by a general strategy. Key building blocks are enantiomerically pure lactones of type A with a leaving group Y which can be pre
Controlled syntheses of 12-oxo-PDA and its 13-epimer
Kobayashi, Yuichi,Matsuumi, Michitaka
, p. 4361 - 4364 (2007/10/03)
Stereoselective synthesis of 12-oxo-PDA starting with (1R,3S)-cyclopenten-1,3-diol monoacetate is accomplished. Key transformations are copper-catalyzed installation of the C(1)-C(8) chain onto the cyclopentene ring and construction of the C(14)-C(18) cha
Biological activity and biosynthesis of pentacyclic oxylipins: The linoleic acid pathway
Gundlach, Heidrun,Zenk, Meinhart H.
, p. 527 - 537 (2007/10/03)
The relevance of the postulated pathway from linoleic acid to dihydrojasmonic acid is analysed. Pentacyclic oxylipins having pentenyl or pentyl side chains were tested for their secondary metabolite inducing activity in seven different plant cell culture species which all responded well to 12-oxo-phytodienoic acid and jasmonic acid. The response towards the dihydro-derivatives 15,16-dihydro-12-oxo-phytodienoic acid and 9,10- dihydrojasmonic acid ranged from strong activity in Eschscholzia californica to no activity in Lycopersicon esculentum. 15,16-Dihydro-12-oxo-phytodienoic acid can be formed from linoleic acid (18:2) by a linseed acetone powder enzyme preparation. Application experiments with linoleic (18:2) and linolenic acid (18:3) showed that the bottleneck of the 18:2 pathway is most likely the cyclization of the intermediate allene oxide when compared to the ease by which 15,16-dihydro-12-oxo-phytodienoic acid is converted to dihydrojasmonic acid in plant systems. The metabolism of potential precursors of jasmonic and dihydrojasmonic acid was extensively studied in various cell cultures.
Synthesis of -Linoleic acid and its Use to Confirm the Pathway to 12-Oxophytodienoic acid (12-oxoPDA) in Plants: A Conspectus of the Epoxycarbonium Ion Derived Family of Metabolites from Linoleic and Linolenic Acid Hydroperoxides
Crombie, Leslie,Morgan, David O.
, p. 581 - 587 (2007/10/02)
Using acetylene methodology, a synthesis of -octadeca-9(Z),12(Z),15(Z)-trienoic acid is described.The isotopically marked acid is used to distinguish decisively between two possible pathways for the formation of 12-oxophtytodienoic acid (12-oxoPDA) by flax enzyme preparation in plants: (a) a route via antarafacial ring closure of a zwitterion derived from an allene epoxide (no loss of 14,14-2H2) and (b) a pathway resembling the accepted mammalian prostaglandin biosynthesis (loss of one 14-2H).Pathways to metabolic products formed in Nature from linoleic and linolenic acid are summarised in Scheme 3.The entry species is considered to be the epoxy-carbonium ion.Loss of a proton leads to an allene-epoxide from which are formed the α-ketol, the γ-ketol and 12-oxoPDA.A second group of products (colneleic and colnelenic acid, a hemiacetal, its corresponding aldehydes and an epoxy alcohol) are not formed via the allene-epoxide.The epoxy-carbonium ion can be trapped as an epoxy alcohol or rearranged via a vinyl-oxonium ion with capture by water to form a hemiacetal.Alternatively, loss of a proton from the epoxy-carbonium ion or vinyl-oxonium ion leads to colneleic and colnelenic acid.
Synthesis of 12-Oxophytodienoic Acid (12-OxoPDA) and the Compounds of its Enzymic Degradation Cascade in Plants, OPC-8:0, -6:0, -4:0 and -2:0 (epi-Jasmonic Acid), as their Methyl Esters
Crombie, Leslie,Mistry, Kamlesh M.
, p. 1981 - 1991 (2007/10/02)
The synthesis of 12-Oxophytodienoic acid, and the compounds of its enzymatic degradation sequence, OPC-8:0, -6:0, -4:0 and -2:0, important plant metabolites derived from linolenic acid, is reported.The syntheses use the known cyclopent-3-ene-1,2-diacetic acid as an early intermediate, and this is derived from the Cope rearrangement of 5-vinyltrinorborn-2-ene via bicyclonona-3,7-diene.Iodolactonisation and tributyltin hydride reduction provides the key intermediate (3-oxo-2-oxabicyclooctan-6-yl)acetic acid for the OPC series, whilstphenylselenolactonisation and elimination provides the necessary unsaturated lactone (7-oxo-8-oxabicyclooct-2-en-4-yl)acetic acid for 12-oxoPDA.Members of the OPC-series were made by chain extending the saturated oxabicyclooctane acid: that for the OPC-4:0 involved double Arndt-Eistert reaction, whilst the intermediates for OPC-6:0 and -8:0 were made by Kolbe anodic crossed coupling.The lactones were than converted via their lactols, Wittig reaction, esterfication and oxidation, into the compounds of the OPC ester series, including OPC-2:0 (methyl epi-jasmonate).The unsaturate lactone 8-(7-oxo-8-oxabicyclooct-2-en-4-yl)octanoic acid required for 12-oxoPDA synthesis could also be prepared by anodic synthesis either from (7-oxo-8-oxa-bicyclooct-2-en-4-yl)acetic acid, or from its 2-phenylseleno-2,3-dihydro precursor as elimination occurred concomitantly during the reaction.Since yields were low, the unsaturated acid lactone was converted into its lactol and the (Z)-pent-2-enyl side-chain was inserted first.After TBDMS blocking of the cyclopentene hydroxy group, the side-chain was elaborated to give5-(pent-2-enyl)cyclopent-2-enylacetaldehyde and chain extension carried out by a Grignard-demesylation procedure.Sequential desilylation and depyranylation, followed by oxidation of the diol, gave 12-oxoPDA, isolated as its methyl ester.
Cycloalkenone Synthesis via Lewis Acid Catalyzed Retro Diels-Alder Reactions of Norbornene Derivatives: Synthesis of 12-Oxophytodienoic Acid
Grieco, Paul A.,Abood, Norman
, p. 6008 - 6010 (2007/10/02)
Norbornene derivatives of type 1 undergo retro Diels-Alder reactions at or below ambient temperature in the presence of methylaluminium dichloride and a reactive dienophile.Application of the cycloreversion methodology to the synthesis of 12-oxophyt
