Submitted to: Meeting Abstract
Publication Type: Abstract Only
Publication Acceptance Date: 8/14/2014
Publication Date: 8/14/2014
Citation: Compton, D.L., Laszlo, J.A., Appell, M.D., Evans, K.O. 2014. Synthesis, isolation, and acyl migration kinetics of desaturated and hydroxylated 2-monoacylglycerols [abstract]. American Chemical Society. Abstract AGFD292.
Technical Abstract: 2-Monoacylglycerols (2-MAG) are key synthetic intermediates used for the synthesis of structured lipids with specific, functionalized fatty acids in the sn-2 glycerol position. These sn-ABA-type structured lipids are an integral part of research conducted to understand human physiological effects of the gut, liver and brain. A series of 2-MAG were synthesized by the enzyme-catalyzed alcoholysis of triacylglycerols and isolated by flash chromatography. The affect of desaturation and hydroxylation on 2-MAG spontaneous acyl migration was investigated. Density functional modeling of C18:1, C18:2, C18:3, and C18:1,-OH 2-MAG predicted that desaturation and hydroxylation had little effect on acyl migration and yielded activation energies of 36.26, 35.65, 37.18, and 37.44 kJ mol-1, respectively. 1H NMR kinetic measurements yielded relative energies of activation two fold higher than the predicted values, 73.3, 68.0, 72.9 and 82.9 kJ mol-1, respectively, and confirmed that desaturation and hydroxylation at = C9 had little effect on spontaneous acyl migration.