title: Cyclopentanoids from cyclopentadiene: synthesis of (-)-methyl jasmonate and (+)-12-oxophytodienoic acid.
abstract: 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.
authors: Faculty of Engineering, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan. nogami@dac.ous.ac.jp
authors: Junzo
authors: J
authors: Nokami
authors: Kazuhiko
authors: K
authors: Fujii
authors: Yusuke
authors: Y
authors: Mizutani
authors: Rikiya
authors: R
authors: Omatsu
authors: Kiyoshi
authors: K
authors: Watanabe
authors: Hiroshi
authors: H
authors: Yasuda
authors: Tsutomu
authors: T
authors: Inokuchi
mesh_terms: D000085:Acetates / Q000138:chemical synthesis*; D003517:Cyclopentanes / Q000138:chemical synthesis*; D005231:Fatty Acids, Unsaturated / Q000138:chemical synthesis*; D054883:Oxylipins / Q000138:chemical synthesis*
chemical_list: D000085:Acetates; D003517:Cyclopentanes; D005231:Fatty Acids, Unsaturated; D054883:Oxylipins; C025999:12-oxophytodienoic acid; C072239:methyl jasmonate