Application of allylic substitutions in natural products synthesis

Synthesis routes are described, allowing all known jasmonoids as well as their enantiomers to be synthesized in enantiomerically and diastereomerically pure form. The routes are based on a set of closely related lactones containing an electrophilic allylic moiety, which are accessible via asymmetric...

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Bibliographic Details
Published inPure and applied chemistry Vol. 76; no. 3; pp. 495 - 505
Main Authors Helmchen, G., Ernst, Martin, Paradies, G.
Format Journal Article
LanguageEnglish
Published Berlin De Gruyter 01.01.2004
Walter de Gruyter GmbH
Subjects
Alkylation
Archaea
Chemical compounds
Chemical reactions
Enantiomers
Lactones
Lipids
Natural products
Stereoselectivity
Synthesis
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Summary:Synthesis routes are described, allowing all known jasmonoids as well as their enantiomers to be synthesized in enantiomerically and diastereomerically pure form. The routes are based on a set of closely related lactones containing an electrophilic allylic moiety, which are accessible via asymmetric Pd-catalyzed allylic alkylation. Regio- and diastereoselective S 2'- -reactions of the electrophilic lactones with organocopper compounds furnished 2,3- -disubstituted cyclopentenones, which were further transformed into the target compounds, i.e., 12-oxophytodienoic acid (12-OPDA) in excellent overall yields. The methodology also allowed iridoids and isoprostanes to be prepared. The configuration of an membrane lipid constituent containing cyclopentane rings was determined by total synthesis of a diol that was also obtained by degradation of the natural product.
ISSN:0033-4545
1365-3075
DOI:10.1351/pac200476030495