Facile determination of the absolute stereochemistry of hydroxy fatty acids by GC: application to the analysis of fatty acid oxidation by a P450(BM3) mutant

Cryle, Max J. and De Voss, James J. (2007) Facile determination of the absolute stereochemistry of hydroxy fatty acids by GC: application to the analysis of fatty acid oxidation by a P450(BM3) mutant. Tetrahedron: Asymmetry, 18 4: 547-551. doi:10.1016/j.tetasy.2007.01.034


Author Cryle, Max J.
De Voss, James J.
Title Facile determination of the absolute stereochemistry of hydroxy fatty acids by GC: application to the analysis of fatty acid oxidation by a P450(BM3) mutant
Formatted title
Facile determination of the absolute stereochemistry of hydroxy fatty acids by GC: application to the analysis of fatty acid oxidation by a P450BM3 mutant
Journal name Tetrahedron: Asymmetry   Check publisher's open access policy
ISSN 0957-4166
Publication date 2007-03-07
Sub-type Article (original research)
DOI 10.1016/j.tetasy.2007.01.034
Volume 18
Issue 4
Start page 547
End page 551
Total pages 5
Place of publication Oxford
Publisher Pergamon-elsevier Science Ltd
Collection year 2008
Language eng
Subject 250301 Organic Chemical Synthesis
C1
780103 Chemical sciences
Abstract The determination of the absolute stereochemistry of hydroxy fatty acid methyl esters as their (S)-ibuprofen esters is possible via standard gas chromatographic techniques. Analyses of various racemic and nonracemic standards and mixtures from enzymic oxidation show excellent resolution of the resultant diastereomers, with the (S,S)-diastereomers eluting first in all cases studied. The stereochemistry of the oxidation of dodecanoic acid by P450(BM3), which has not been previously reported, was determined by this method and indicated a preference for (R)-hydroxylation. The sensitivity of this technique allows the analysis of very small quantities of product, which has revealed that the oxidation of dodecanoic and hexadecanoic acids by the T268A mutant of P450(BM3) display the same stereochemical efficiency and produce (R)-hydroxy fatty acids in the same manner as wildtype P450(BM3), despite the poor coupling efficiency of these substrates. This stereochemistry implies that hydroxylation catalysed by the T268A mutant of P450(BM3) occurs through residual levels of the normal hydroxylating species. (c) 2007 Elsevier Ltd. All rights reserved.
Keyword Chemistry, Inorganic & Nuclear
Chemistry, Organic
Chemistry, Physical
Cytochrome P450-catalyzed Reactions
Electrophilic Oxidant
Oxygen Activation
P450bm-3
Intermediate
Cyclopropyl
Epoxidation
Mutagenesis
Catalysis
Olefins
Q-Index Code C1
Q-Index Status Confirmed Code

 
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Created: Mon, 18 Feb 2008, 16:54:50 EST