Tandem reduction-chloroallylboration of esters: Asymmetric synthesis of lamoxirene, the spermatozoid releasing and attracting pheromone of the laminariales (Phaeophyceae)

被引：16

作者：

Hertweck, C ^{[1
]}

Boland, W ^{[1
]}

机构：

[1] Max Planck Inst Chem Ecol, D-07745 Jena, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2000年 / 65卷 / 08期

关键词：

D O I：

10.1021/jo991629r

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The asymmetric synthesis of all four stereoisomers of lamoxirene (cis-2-cyclohepta-2,5-dienyl-3-vinyloxirane), the spermatozoid-releasing and -attracting pheromone of the Laminariales (Phaeophyceae), is reported. Chiral ethyl cyclohepta-2,5-diene carboxylates, prepared by a divinylcyclopropane Cope rearrangement, were effectively alkylated by means of a novel tandem DIBAL-H reduction/asymmetric alpha-chloroallylboration using (Z)-gamma -chloroallyldiisopinocampheylboranes. The ensuing syn-alpha-chlorohydrins were transformed into the corresponding vinyloxiranes with DBU, providing all four isomers bf the pheromone in good chemical and excellent optical yield (90-97% eel. Spermatozoid-release assays were conducted with the sympatrically growing species L. digitata, L. hyperborea, and L. saccharina and established (1'S,2R,3S)-1c as the most active isomer in all cases.

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页码：2458 / 2463

页数：6

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