Nokami Junzo, Fujii Kazuhiko, Mizutani Yusuke, Omatsu Rikiya, Watanabe Kiyoshi, Yasuda Hiroshi, Inokuchi Tsutomu
Faculty of Engineering, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan.
Nat Prod Commun. 2013 Jul;8(7):919-23.
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.
亚油酸代谢产物（-）-茉莉酸甲酯和（+）-12-氧代植物二烯酸（（+）-12-氧代-PDA）由相同的前体（1,2-反式，1,3-顺式，2'Z）-2-（戊-2'-烯基）-环戊-4-烯-1,3-二醇制备，该前体通过环戊二烯的区域选择性戊-2-烯基化以及随后光氧化为顺式-1,3-二醇而获得。通过将源自（1R,2S,3S,2'Z）-3-乙酰氧基-2-（戊-2'-烯基）环戊-4-烯-1-醇的π-烯丙基钯中间体与丙二酸二甲酯烷基化，将甲氧基羰基甲基取代基引入环戊烷环以制备（-）-茉莉酸甲酯。通过将（1S,2R,3R,2'Z）-3-乙酰氧基-2-（戊-2'-烯基）环戊-4-烯-1-醇与二烃基铜酸盐进行S(N)2型亲核取代，将α-链引入环戊烷环以制备（+）-12-氧代-PDA。
