Linoleic acid metabolites (-)-methyl jasmonate and (+)-12-oxophytodienoic acid ((+)-12-oxo-PDA) were prepared from the same precursor (1,2-trans, 1,3-cis, 2′Z)-2-(pent-2′-enyl)-cyclopent-4-en-1,3-diol which was obtained by regioselective pent-2-enylation of cyclopentadiene and following photooxidation to cis −1,3-diol. A methoxycarbonylmethyl substituent was introduced to the cyclopentane ring via alkylation of the π-allyl palladium intermediate derived from (1 R,2S,3S,2′Z)-3-acetoxy-2-(pent-2′-enyl)cyclopent-4-ene-1-ol with dimethyl malonate for (-)-methyl jasmonate. The α-chain was introduced to the cyclopentane ring via the SN2 type nucleophilic substitution of (1S,2R,3R,2′Z)-3-acetoxy-2-(pent-2′-enyl)cyclopent-4-ene-1-ol with a dialkylcuprate for (+)-12-oxo-PDA.
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