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J Org Chem

Title:		"Stereospecificity of an enzymatic monoene 1,4-dehydrogenation reaction: conversion of (Z)-11-tetradecenoic acid into (E,E)-10,12-tetradecadienoic acid"
Author(s):		Rodriguez S; Clapes P; Camps F; Fabrias G;
Address:		"Department of Biological Organic Chemistry and Deparment of Peptide and Protein Chemistry, IIQAB-CSIC, Jordi Girona 18-26, 08034-Barcelona, Spain"
Journal Title:		J Org Chem
Year:		2002
Volume:		67
Issue:		7
Page Number:		2228 - 2233
DOI:		10.1021/jo0109927
ISSN/ISBN:		0022-3263 (Print) 0022-3263 (Linking)
Abstract:		"In this article, we report the first stereochemical study of an enzymatic 1,4-dehydrogenation reaction, namely, the transformation of (Z)-11-tetradecenoic acid into (E,E)-10,12-tetradecadienoic acid, involved in the sex pheromone biosynthesis of the moth Spodoptera littoralis. The investigation was carried out using the labeled substrates (R)-[10-(2)H]- and (S)-[10-(2)H]-tridecanoic acids ((R)-2 and (S)-2, respectively) and (R)-[2,2,3,3,13-(2)H(5)]- and (S)-[2,2,3,3,13-(2)H(5)]-tetradecanoic acids ((R)-1 and (S)-1, respectively). Probes (R)-2 and (S)-2 were prepared as described in a previous article.(1) The synthesis of the pentadeuterated chiral substrates (R)-1 and (S)-1 was accomplished by kinetic resolution of the racemic 12-tridecyn-2-ol (6) with immobilized porcine pancreatic lipase. The enantiomerically pure alcohols (R)-6 and (S)-6 were transformed into the final acids (S)-1 and (R)-1, respectively, by a sequence of well-established reactions. The analyses of methanolyzed lipidic extracts from glands incubated separatedly with each individual probe showed that in the transformation of (Z)-11-tetradecenoic acid into (E,E)-10,12-tetradecadienoic acid, both pro-(R) hydrogen atoms at C-10 and C-13 are removed from the substrate. This is the first example reported of a desaturase with pro-(R)/pro-(R) stereospecificities that gives rise to (E)-double bonds. A mechanistic explanation for the stereochemical outcome of this reaction is advanced"
Keywords:		"Animals Aspergillus niger/enzymology Binding Sites Candida/enzymology Catalysis Fatty Acids, Monounsaturated/chemistry/*metabolism Kinetics Lipase/*metabolism Magnetic Resonance Spectroscopy Molecular Structure Moths/*metabolism Myristic Acids/chemistry/*;"
Notes:		"MedlineRodriguez, Sergio Clapes, Pere Camps, Francisco Fabrias, Gemma eng Research Support, Non-U.S. Gov't 2002/04/02 J Org Chem. 2002 Apr 5; 67(7):2228-33. doi: 10.1021/jo0109927"