12-Oxophytodienoic acid

Cycloalkenones.3 Cycloalkenones can be prepared by a retro Diels-Alder reaction of norbornenes of type 1, conducted at 25-70° in the presence of CH3A1C12 (1 equiv.) and a reactive dienophile, usually maleic anhydride or fumaronitrile. The [4 + 2]cycloreversion was used to prepare 12-oxophytodienoic acid (4), which epi-merizes at Cu to the trans-isomer on brief exposure to acid. The precursor nor-bornene 3 was prepared from the known dienone 2 as shown. Treatment of 3 at room... 

Fig. 2. Schematic representation of the jasmonate biosynthetic pathway 12-oxo-PDA 12-Oxophytodienoic acid HPOT 13(S)-hydroperoxyoctadecatrienoic acid EOT 12,13(S)-epoxyoctadecatrienoic acid MeJA methyl jasmonate. Chiral centers have been excluded from the names for clarity. The figure is adapted from Mueller [52]...

SOBAJIMA, H., TAKEDA, M., SUGIMORI, M., KOBASHl, N., KIRIBUCHI, K., CHO, E.M., AKIMOTO, C., YAMAGUCHI, T., MINAMI, E., SHIBUYA, N., SCHALLER, F., WEILER, E.W., YOSHIHARA, T., NISHIDA, H., NOJIRI, H., OMORI, T., NISHIYAMA, M., YAMANE, H., Cloning and charaeterization of a jasmonic acid-responsive gene encoding 12-oxophytodienoic acid reductase in suspension-cultured rice cells, Planta, 2003, 216,692-698. 

Jasmonic acid is derived from a-linolenic acid, 13(5)-hydroperoxylinolenic acid, 12-oxophytodienoic acid, and phytodienoic acid (Farmer and Ryan, 1990, 1992 Hamberg and Gardner, 1992). The biosynthesis of jasmonic acid and related compounds has been reviewed (Sembdner and Parthier, 1993). 

Crombie, L. and K. M. Mistry, 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, J. Chem. Soc. Perkin Trans. I, 1981-1991 (1991). 

Fig. 1.3. Biosynthesis of the Unolenate metabolite and plant growth regulator, jasmonic acid. Abbreviations used are LOX, lipoxygenase AOS, allene oxide synthase AOC allene oxide cyclase p-OX 12-oxophytodienoic acid reductase and p-oxidase. Based on diagrams published in ref. 15.

The structure of the oxophytodienoic acid-containing galactolipid from Arabidopsis thaliana... 

Buseman, C.M., Tamura, R, Sparks, A.A., Baughman, E.J., Maatta, S., Zhao, J., Roth, M.R., Esch, S.W., Shah, J., Wilhams, T.D. and Welti, R. (2006) Wounding stimulates the accumulation of glycerohpids containing oxophytodienoic acid and dinor-oxophytodienoic acid in Arabidopsis leaves. Plant Physiol. 142, 28-39. 

Fig. 22.2 Consensus effects of Spd and Spm on jasmonic acid metaboUsm and signaling cascade. Description same as in legend to Fig. 22.1.12-OH-JA 12-hydoxyjasmonic acid, AOC aUene oxide cyclase, COIl coronatine insensitive 1, /A-/fe jasmonate (JA)-isoleudne conjugate, JARl jasmo-nate resistant 1, 7AZ jasmonate-zim-domain protein, 7J jasmonate response element, JRFS jasmonate response factors, KAT 3-keto-acyl-coenzyme A thiolase, LOX lipoxygenase, MYC and TGA transcription factor proteins, OPDA cw-(+)-12-oxophytodienoic add, OPR3 oxophytodieno-ate reductase 3, ST2A and ST2B sulfotransferase...

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