Synthesis and Use of Probes to Investigate the Cryptoregiochemistry of the First Animal Acetylenase

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• 作者：José ; -Luis Abad ; Sergio Rodr&iacute ; guez ; Francisco Camps ; Gemma Fabrià ; s
• 刊名：Journal of Organic Chemistry
• 出版年：2006
• 出版时间：September 29, 2006
• 年：2006
• 卷：71
• 期：20
• 页码：7558 - 7564
• 全文大小：132K
• 年卷期：v.71,no.20(September 29, 2006)
• ISSN：1520-6904

文摘

Thaumetopoea pityocampa pheromone glands contain an unusual ¹¹ acetylenase that produces an alkynoicfatty acid intermediate in the sex pheromone biosynthetic pathway of this species. In this article, wedescribe the synthesis and use of the deuterated (Z)-11-hexadecenoic acid probes required to decipherthe cryptoregiochemistry of this enzyme. The label in the olefinic bonds was introduced by Wittig reactionbetween the appropriate deuterated reagents. Besides the vinyl deuterium atoms, for reliable GC-MSanalyses these compounds bear a tetradeuterium tag, which was introduced by deuteration of an alkyneintermediate in the presence of the Wilkinson catalyst. Pheromone gland metabolization studies of theseprobes provided experimental evidence that the transformation of (Z)-11-hexadecenoic acid into 11-hexadecynoic acid by the ¹¹ acetylenase takes place by a stepwise mechanism, in which a significantperturbation of the strong vinyl C11-H bond occurs prior to a fast elimination of the vinyl hydrogen atC-12.