Synthesis of sphingomyelin and its analogs.
Item
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Title
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Synthesis of sphingomyelin and its analogs.
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Identifier
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AAI9108169
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identifier
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9108169
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Creator
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Ruan, Zhong-shi.
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Contributor
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Adviser: Robert Bittman
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Date
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1990
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Organic
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Abstract
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Sphingomyelin and its analogs are synthesized for use in biophysical studies, especially for kinetic studies of the movement of cholesterol between membranes, and for analysis of sphingomyelin and cholesterol interactions. In this thesis sphingomyelin is prepared from DL-erythro-sphingosine, which is prepared in an aldol condensation of tris(trimethylsilyl)glycine with (E)-hexadec-2-enal followed by lithium aluminum hydride reduction. The diastereoselectivity of the aldol condensation is determined by chiral high-pressure liquid chromatography of the biphenylcarboxamido and (R)-(+)-{dollar}\alpha{dollar}-methoxy-{dollar}\alpha{dollar}-(trifluoromethyl)phenylacetic acid ester derivatives of sphingosine. The ratio of erythro- to threosphingosines is 98.0:2.0, and the ratio of D- to L-erythro isomer is 50:50, both based on integration of the peak areas. Three different phosphorylation or phosphitylation reagents are used for the conversion of ceramide to sphingomyelin; they are 2-chloro-2-oxo-1,3,2-dioxaphospholane, 2-bromoethylphosphoric acid dichloride, and N,N-diisopropylmethylphosphoramidic chloride. The syntheses of sphingomyelin and analogs such as 3-O-alkylsphingomyelins (3-O-methyl and 3-O-ethyl-DL-erythro-sphingomyelins) and 3-deoxy-DL-sphingomyelin, isotopically labeled sphingomyelins ( (4,5-{dollar}\sp2{dollar}H{dollar}\sb2{dollar}) -DL-erythro-sphingomyelin and {dollar}\sp{15}{dollar}N-DL-erythro-sphingomyelin), and different N-acyl sphingomyelins (N-dodecanoyl-, N-tetradecanoyl-, N-octadecanoyl-, N-docosanoyl-, N-tetracosanoyl-, N-(cis-15-tetracosenoyl)-, and N- ((2{dollar}\sp\prime{dollar}R,S)-hydroxyhexadecanoyl) -DL-erythro-sphingomyelins) are described in detail.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
