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Synthesis of fluorinated analogs of myristic acid as potential inhibitors of egyptian armyworm (Spodoptera littorialis) Δ11 desaturasedesaturase

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Lipids

Abstract

To study the activity of the different desaturases present in the pheromone biosynthetic pathway of the Egyptian armyworm, Spodoptera littoralis, we prepared a series of mono-and gem-difluorinated analogs of myristic acid with halogen substitution at the C8–C11 positions of the aliphatic chain via specifically positioned dithiane precursors. Thus, transformation of dithianes by treatment with N-bromosuccinimide in the presence of H2O followed by reduction with LiAIH4 afforded the appropriate alcohols, which reacted with diethylaminosulfur trifluoride to give rise to the corresponding monofluoroderivative intermediates. Alternatively, the introduction of the gem-difluoro functionality was carried out by reaction of the appropriate dithiane intermediate with 1,3-dibromo-5,5-dimethylhydantoin in the presence of HF/pyridine. The activity of these fluorinated FA as substrates and inhibitors of the desaturases involved in the biosynthesis of the sex pheromonal blend of S. littoralis has been studied. In this case, 11-fluorotetradecanoic acid elicited a moderate inhibitory activity of Δ11 desaturase.

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Abbreviations

DAST:

diethylaminosulfur trifluoride

DEPT:

distortionless enhancement by polarization transfer

FA:

fatty acid

MTBE:

methyl tert-butyl ether

NBS:

N-bromosuccinimide

SIM:

selected ion monitoring

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Authors and Affiliations

  1. Departmento de Química Orgánica Bjológica, (IIQAB, CSIC), Jordi Girona 18-26, 08034, Barcelona, Spain

    José-Luis Abad, Gemma Villorbina, Gemma Fabriàs & Francisco Camps

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  1. José-Luis Abad
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  2. Gemma Villorbina
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  3. Gemma Fabriàs
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  4. Francisco Camps
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Correspondence to Francisco Camps.

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Abad, JL., Villorbina, G., Fabriàs, G. et al. Synthesis of fluorinated analogs of myristic acid as potential inhibitors of egyptian armyworm (Spodoptera littorialis) Δ11 desaturasedesaturase. Lipids 38, 865–871 (2003). https://doi.org/10.1007/s11745-003-1137-2

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  • DOI: https://doi.org/10.1007/s11745-003-1137-2

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