136845-14-2Relevant articles and documents
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.
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.
Efficient Syntheses of the OPC Homologous Series, OPC-1:0, -3:0, -4:0, -5:0, -6:0, -7:0, and -8:0
Toshima, Hiroaki,Nara, Shinji,Aramaki, Hisateru,Ichihara, Akitami,Koda, Yasunori,Kikuta, Yoshio
, p. 1724 - 1728 (2007/10/03)
The OPC homologous series was synthesized from 2-[(Z)-2-pentenyl]cyclopenten-1-one in short steps and with high yields. The carbon-carbon bond formation was achieved by the 1,4-conjugate addition approach. This method makes it possible to supply a suffici
