2024-03-29T06:26:02Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/123412022-03-24T13:49:12Zcom_10261_5063com_10261_5col_10261_5066
Synthesis and Use of Probes to Investigate the Cryptoregiochemistry of the First Animal Acetylenase
Abad, José Luis
Rodríguez Ropero, Sergio
Camps Díez, Francisco
Fabriàs, Gemma
Cryptoregiochemistry
Thaumetopoea pityocampa pheromone glands
Acetylenase
Alkynoic fatty acid
Metabolization
Z-11-hexadecenoic acid
11-hexadecynoic acid
Vinyl hydrogen at C-12
7 pages, 1 table, 4 figures, 2 schemes.
Thaumetopoea 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.
We gratefully acknowledge CICYT and FEDER (AGL2001-0585) and Generalitat de Catalunya (2001SGR 00342) for financial support. J.-L.A. thanks Spanish MEC for a Ramón y Cajal contract. The authors also acknowledge Rodolfo Hernández from Laboratorio de Sanidad Forestal (Gobierno de Aragón, Mora de Rubielos, Teruel) for providing T. pityocampa female pupae.
Peer reviewed
2009-04-16T10:12:25Z
2009-04-16T10:12:25Z
2006-09-29
artículo
http://purl.org/coar/resource_type/c_6501
The Jornal of Organic Chemistry 71(20): 7558-7564 (2006)
0022-3263
http://hdl.handle.net/10261/12341
10.1021/jo060789h
1520-6904
en
http://dx.doi.org/10.1021/jo060789h
none
19968 bytes
application/msword
American Chemical Society