文章基本信息

标题：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.
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作者：A Kisic ; M Tsuda ; R J Kulmacz 等
期刊名称：JLR Papers In Press
印刷版ISSN：0022-2275
电子版ISSN：1539-7262
出版年度：1995
卷号：36
期号：4
页码：787-803
语种：English
出版社：American Society for Biochemistry and Molecular Biology
摘要：As described by Carter et al. (J. Biol. Chem. 1951. 192: 197-207), O-methyl derivatives of sphingosine are formed upon acid hydrolysis of sphingolipids in the presence of methanol. In the present study, we have isolated four O-methyl ethers of C18-sphingosine by medium pressure liquid chromatography of their diacetate derivatives, i.e., (2S,3R,4E)-1-acetoxy-2-acetamido-3-methoxy-4-octadecene, its (2S,3S) epimer, (2R,3E,5R)-1-acetoxy-2-acetamido-5-methoxy-3-octadecene, and its (2R,5S) epimer. Structures were determined by physical, chromatographic, and spectral properties. The 5-O-methyl ethers, which were the predominant byproducts of sphingolipid hydrolysis, were easily distinguished from the 3-O-methyl ethers by chromatography, and all four isomers could be differentiated by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. NMR analysis of the original N-acetate and diacetate samples of O-methylsphingosines I and II of Carter et al. demonstrated that they correspond to the 5-O-methyl ethers (2R,5R and 2R,5S, respectively), with purities of approximately 90-99%. Resolution enhancement of the 126-MHz 13C NMR spectra of the O-methyl ethers and D-erythro-C18-sphingosine (Ia) afforded distinct signals for nearly all carbon atoms. 13C NMR assignments of carbons 7-15 were made from their lanthanide-induced shifts, and revised assignments for olefinic carbons of Ia were established based upon 1H-13C shift correlation experiments.