Sphingolipid bases. A revisitation of the O-methyl derivatives of sphingosine. Isolation and characterization of diacetate derivatives, with revised 13C nuclear magnetic resonance assignments for D-erythro-sphingosine.

Kisić, Alemka; Tsuda, Mitsuhiro; Kulmacz, Richard J.; Wilson, William K.; Schroepfer, George J.

doi:10.1016/s0022-2275(20)40063-x

Cited by 21 publications

(14 citation statements)

References 55 publications

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“…Materials and methods d -Erythro -sphingosine ( 1a ), l -threo -sphingosine ( 3a ), and d -erythro -dihydrosphingosine ( 5a ) were isolated from cow brain as described previously (10,11) and showed high purity by TLC and 1 H NMR. l -Erythro -sphingosine ( 2a ) was purchased from Sigma (St. Louis, MO) and showed у 99% purity by NMR as the MTPA derivative 2b .…”

Section: Experimental Procedures and Resultsmentioning

confidence: 99%

“…d -Erythro -sphingosine ( 1a ; Fig. 1 ) has traditionally been isolated from natural sources (10,11), but total synthesis has become an important alternative (12-17 and references therein). A potential problem with total synthesis is the formation of stereoisomeric mixtures.…”

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confidence: 99%

“…A potential problem with total synthesis is the formation of stereoisomeric mixtures. Diastereomeric impurities can generally be detected by thinlayer chromatography (TLC), gas chromatography (GC), or nuclear magnetic resonance (NMR) spectroscopy (10) and removed by chromatographic methods. Enantiomeric impurities, by contrast, are difficult to remove and to detect.…”

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confidence: 99%

“…Optical rotation, the classical method for measuring the enantiomeric purity of sphingosine samples, suffers from low precision and numerous potential sources of er-ror (18). These problems are exacerbated by the low specific rotation of sphingosine and its N -acetate and triacetate derivatives (10). Circular dichroism spectra, from which sphingosine and dihydrosphingosine isomers can be identified (19), would be subject to similar (albeit fewer) sources of error for determining enantiomeric purity.…”

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confidence: 99%

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New methods for determining the enantiomeric purity of erythro-sphingosine

Wilson

Schroepfer

1999

Journal of Lipid Research

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The enantiomeric purity of erythro -sphingosine samples can be determined simply, reliably, and accurately from 1 H or 19 F nuclear magnetic resonance spectra of the ␣ -methoxy-␣ -(trifluoromethyl)phenylacetate (MTPA) derivative. As little as 0.1% of the minor enantiomer could be observed in a 1-mg sample, and detection limits of 1% and 5% were estimated for samples of 100 g and 10 g. The two threo -sphingosine enantiomers and four dihydrosphingosine stereoisomers were also differentiated by this technique, which served as an effective method for assessing the purity of sphingosine and dihydrosphingosine samples. Enantiomeric and diastereomeric purities could also be determined by normal-phase high performance liquid chromatographic analysis of the MTPA derivatives. -Li, S., W. K. Wilson, and G. J. Schroepfer, Jr. New methods for determining the enantiomeric purity of erythro -sphingosine. J.

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Section: Experimental Procedures and Resultsmentioning

confidence: 99%

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confidence: 99%

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New methods for determining the enantiomeric purity of erythro-sphingosine

Wilson

Schroepfer

1999

Journal of Lipid Research

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“…CDCl 3 -D 2 O designates addition of a drop of D 2 O to a CDCl 3 solution to improve spectral definition. 4 COSY( 1 H-1 H correlation spectroscopy), HSQC (heteronuclear single quantum coherence), and heteronuclear multiple bond correlation (HMBC) spectra were acquired as described previously (28). Most 1 H NMR chemical shifts from CDCl 3 solutions are presented to Ϯ 0.001 ppm precision and are corrected for effects of strong coupling.…”

Section: Methodsmentioning

confidence: 99%

Chemical synthesis of d-ribo-phytosphingosine-1-phosphate, a potential modulator of cellular processes

Wilson

Schroepfer

1999

Journal of Lipid Research

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D -erythro -Sphingosine-1-phosphate ( 2 ), an intermediate in sphingosine metabolism, shows a diversity of biological activities. Comparable roles might be anticipated for D -ribo -phytosphingosine-1-phosphate ( 1 ). We describe an efficient three-step chemical synthesis of 1 from D -ribophytosphingosine. Our approach is based on standard phosphoramidite methodology and on the finding of Boumendjel and Miller ( J. Lipid Res. 1994. 35: 2305-2311) that sphingosine can be monophosphorylated at the 1-hydroxyl without protection of the 3-hydroxyl. However, we were unable to duplicate their reported synthesis of 2 without important modifications in reagents and reaction conditions. Under the reported conditions for preparing 2 , we obtained a cyclic carbamate ( 14), which we have isolated and identified. The structures of 1 and the cyclic carbamate 14 were elucidated by a combination of mass spectrometry and 1D and 2D nuclear magnetic resonance spectroscopy.-Li, S., W. K. Wilson, and G. J. Schroepfer, Jr. Chemical synthesis of D -ribo -phytosphingosine-1-phosphate, a potential modulator of cellular processes.

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