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Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/12341
Título

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

AutorAbad, José Luis; Rodríguez Ropero, Sergio; Camps Díez, Francisco; Fabriàs, Gemma
Palabras claveCryptoregiochemistry
Thaumetopoea pityocampa pheromone glands
Acetylenase
Alkynoic fatty acid
Metabolization
Z-11-hexadecenoic acid
11-hexadecynoic acid
Vinyl hydrogen at C-12
Fecha de publicación29-sep-2006
EditorAmerican Chemical Society
CitaciónThe Jornal of Organic Chemistry 71(20): 7558-7564 (2006)
ResumenThaumetopoea pityocampa pheromone glands contain an unusual Δ11 acetylenase that produces an alkynoic fatty acid intermediate in the sex pheromone biosynthetic pathway of this species. In this article, we describe the synthesis and use of the deuterated (Z)-11-hexadecenoic acid probes required to decipher the cryptoregiochemistry of this enzyme. The label in the olefinic bonds was introduced by Wittig reaction between the appropriate deuterated reagents. Besides the vinyl deuterium atoms, for reliable GC−MS analyses these compounds bear a tetradeuterium tag, which was introduced by deuteration of an alkyne intermediate in the presence of the Wilkinson catalyst. Pheromone gland metabolization studies of these probes provided experimental evidence that the transformation of (Z)-11-hexadecenoic acid into 11-hexadecynoic acid by the Δ11 acetylenase takes place by a stepwise mechanism, in which a significant perturbation of the strong vinyl C11−H bond occurs prior to a fast elimination of the vinyl hydrogen at C-12.
Descripción7 pages, 1 table, 4 figures, 2 schemes.
Versión del editorhttp://dx.doi.org/10.1021/jo060789h
URIhttp://hdl.handle.net/10261/12341
DOI10.1021/jo060789h
ISSN0022-3263 (Print)
1520-6904(Online)
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