| Title: | Substrate-dependent stereochemical course of the (Z)-13-desaturation catalyzed by the processionary moth multifunctional desaturase |
| Author(s): | Abad JL; Camps F; Fabrias G; |
| Address: | "Departamento de Quimica OrgAnica Biologica, Instituto de Investigaciones Quimicas y Ambientales de Barcelona, Consejo Superior de Investigaciones Cientificas, 08034 Barcelona, Spain. jlaqob@cid.csic.es" |
| ISSN/ISBN: | 1520-5126 (Electronic) 0002-7863 (Linking) |
| Abstract: | "The stereochemical course of the Delta13 desaturation involved in the biosynthesis of Thaumetopoea pityocampa sex pheromone was studied using stereotopically labeled and tagged palmitic acids as metabolic probes. In the synthetic pathway, a functionalized acetylene common synthon was used for introducing the four deuterium tags. Further coupling of the tetradeuterated synthon to the appropriated alkynol and a double chemoenzymatic strategy to resolve the alcohol functionality allowed one to obtain the enantiomerically enriched probes used in the mechanistic studies. Mass spectrometric analyses of extracts from tissues cultured with each probe revealed that removal of the C13 and C14 hydrogens in 11-hexadecynoate and (Z)-11-hexadecenoate are pro-(R)- and pro-(S)-specific syn-dehydrogenation processes, respectively. This finding constitutes the first example in the literature of an enzymatic (Z)-desaturation exhibiting a substrate-dependent stereochemical course" |
| Keywords: | "Animals Catalysis Deuterium/chemistry Fatty Acid Desaturases/*metabolism Fatty Acids/chemical synthesis/*chemistry/*metabolism Models, Molecular Molecular Structure Moths/*enzymology Stereoisomerism Substrate Specificity;" |
| Notes: | "MedlineAbad, Jose-Luis Camps, Francisco Fabrias, Gemma eng Research Support, Non-U.S. Gov't 2007/11/10 J Am Chem Soc. 2007 Dec 5; 129(48):15007-12. doi: 10.1021/ja0751936. Epub 2007 Nov 9" |
