- Enzymatic preparation of enantiomerically pure sn-2,3-diacylglycerols: A stereoselective ethanolysis approach
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Stereoselective ethanolysis of monoacid TAG by immobilized Rhizomucor miehei lipase (RML) was studied for preparation of optically pure sn-2,3-DAC. Trioctanoylglycerol (TO) was used as a model substrate. The enantiomeric purity of the product, sn-2,3-dioctanoylglycerol (sn-2,3-DO), was very high (percent enantiomeric excess > 99%) when an excess of ethanol was used. The result indicated that RML was highly stereosRMLelective toward the sn-1 position of TO under conditions of excess ethanol. The stereoselectivity of RML depended on the amount of ethanol. The larger the amount of ethanol was, the higher the stereoselectivity became. After optimizing the parameters such as reactant molar ratio, water content, and temperature, (ethanol/TO molar ratio = 31:1 and water content = 7.5 wt% of the reactants at 25°C), optically pure sn-2,3-DO was obtained at 61.1 mol% in the glyceride fraction in 20 min. The above conditions were further applied for ethanolysis of monoacid TAG with different acyl groups such as tridecanoylglycerol (C10:0), tridodecanoylglycerol (C12:0), tritetradecanoylglycerol (C14:0) and trioctadecenoylglycerol [triolein, (C18:1)]. The yields and enantiomeric purities of 1,2(2,3)-DAG were dramatically reduced when TAG with FA longer than decanoic acid were used. Copyright
- Piyatheerawong, Weera,Yamane, Tsuneo,Nakano, Hideo,Iwasaki, Yugo
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- Stereochemical Analysis of Glycerophospholipids by Vibrational Circular Dichroism
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The stereochemistry of glycerophospholipids (GPLs) has been of interest for its roles in the evolution of life and in their biological activity. However, because of their structural complexity, no convenient method to determine their configuration has been reported. In this work, through the first systematic application of vibrational circular dichroism (VCD) spectroscopy to various diacylated GPLs, we have revealed that their chirality can be assigned by the sign of a VCD exciton couplet generated by the interaction of two carbonyl groups. This paper also presents spectroscopic evidence for the stereochemistry of GPLs isolated from bacteria, eukaryotes, and mitochondria.
- Taniguchi, Tohru,Manai, Daisuke,Shibata, Masataka,Itabashi, Yutaka,Monde, Kenji
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p. 12191 - 12194
(2015/10/12)
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- Synthesis and pharmacological evaluation of second-generation phosphatidic acid derivatives as lysophosphatidic acid receptor ligands
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Short-chain phosphatidic acid derivatives, dioctanoyl glycerol pyrophosphate (DGPP 8:0, 1) and phosphatidic acid 8:0 (PA 8:0, 2), were previously identified as subtype-selective LPA1 and LPA3 receptor antagonists. Recently, we report
- Durgam, Gangadhar G.,Tsukahara, Ryoko,Makarova, Natalia,Walker, Michelle D.,Fujiwara, Yuko,Pigg, Kathryn R.,Baker, Daniel L.,Sardar, Vineet M.,Parrill, Abby L.,Tigyi, Gabor,Miller, Duane D.
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p. 633 - 640
(2007/10/03)
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- Acetal phosphate-derived LPA mimics, PPARgamma activators, and autotaxin inhibitors
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Disclosed are compositions that modulate the effects of extracellular LPA receptors, the intracellular PPARγ receptor, and autotaxin, and methods for their use.
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Page/Page column 7; sheet 5
(2010/11/24)
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- Asymmetric Total Synthesis of Phosphatidylinositol 3-Phosphate and 4-Phosphate Derivatives
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New asymmetric syntheses of phosphatidylinositol 3-phosphate (PtdIns(3)P) and phosphatidylinositol 4-phosphate (PtdIns(4)P) derivatives are described. Key intermediates were used to prepare diacylglyceryl moieties with dibutyryl, dioctanoyl, and dihexadecanoyl chains. In addition, a modified route provided PtdIns(3)P and PtdIns(4)P triesters with P-1-linked aminopropyl groups for preparation of affinity probes. The synthesis of the inosityl precursor employed a dibutyltin oxide-mediated p-methoxybenzyl (PMB) etherification to give either the 2-PMB- or the 3-PMB-protected glucopyranosides. The Ferrier rearrangement was used to convert suitably protected glucose derivatives to enantiomerically pure, differentially protected D-myo-inositol key intermediates. A versatile phosphoramidite reagent was employed to allow synthesis of PtdInsPn derivatives with diacylglyceryl moieties of different chain lengths.
- Chen, Jian,Feng, Li,Prestwich, Glenn D.
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p. 6511 - 6522
(2007/10/03)
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