Cyclopentanoids from cyclopentadiene: synthesis of (-)-methyl jasmonate and (+)-12-oxophytodienoic acid.

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 pi-allyl palladium intermediate derived from (1R,2S,3S,2'Z)-3-acetoxy-2-(pent-2'-enyl)cyclopent-4-ene-1-ol with dimethyl malonate for (-)-methyl jasmonate. The alpha-chain was introduced to the cyclopentane ring via the S(N)2 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.

Citation

Junzo Nokami, Kazuhiko Fujii, Yusuke Mizutani, Rikiya Omatsu, Kiyoshi Watanabe, Hiroshi Yasuda, Tsutomu Inokuchi. Cyclopentanoids from cyclopentadiene: synthesis of (-)-methyl jasmonate and (+)-12-oxophytodienoic acid. Natural product communications. 2013 Jul;8(7):919-23

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PMID: 23980424

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