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Methyl-branched octanoic acids as substrates for lipase-catalyzed reactions

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Lipids

Abstract

Hydrolyses of racemic methyl-branched octanoic acid thiolesters are described using six commercial lipases as catalysts. Branching at positions 2, 4 and 5 greatly reduced activity; branching at the 3-position virtually eliminated activity. The reactivities of the racemic branched thiolesters relative to the unbranched ester were very similar for each lipase preparation examined. In reactions involving configurationally pure 2-methyloctanoic acids, the S-enantiomer reacted faster both in esterification of aliphatic alcohols and in hydrolyses of aliphatic alcohol esters with all of the lipases examined. Stereobiases in hydrolyses of the octanoic acid esters branched at other positions were low and variable. In sharp contrast to the hydrolyses of the thiolesters of 2-methyloctanoic acid, two aryl esters of 2-methyloctanoic acid catalyzed byR. miehei lipase hydrolyzed with a bias for the R-configuration. A view of the ester-enzyme complex is offered, to explain the relative rates of reaction of the racemic esters.

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Abbreviations

DTNB:

5,5′-dithio-bis-(2-nitrobenzoic) acid Ellman's reagent

ER :

enantiomeric ratio, ratio of specificity constants for enantiomers

GLC:

gas-liquid chromatography

HMPT:

hexamethylphosphoric triamide

IR:

infrared

2-MOA:

2-methyloctanoic acid

NMR:

nuclear magnetic resonance

R and S:

standard conventions for designating configuration

TLC:

thinlayer chromatography

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Authors and Affiliations

  1. ARS, Eastern Regional Research Center, U.S. Department of Agriculture, 600 East Mermaid Lane, 19118, Philadelphia, PA

    Philip E. Sonnet & Mary Welch Baillargeon

Authors
  1. Philip E. Sonnet
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  2. Mary Welch Baillargeon
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Reference to a brand or firm name does not constitute endorsement by the U.S. Department of Agriculture over others of a similar nature not mentioned.

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Sonnet, P.E., Baillargeon, M.W. Methyl-branched octanoic acids as substrates for lipase-catalyzed reactions. Lipids 26, 295–300 (1991). https://doi.org/10.1007/BF02537140

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  • DOI: https://doi.org/10.1007/BF02537140

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