Chiral synthesis of ether-linked lipids via ring-opening of glycidyl derivatives mediated by boron trifluoride etherate.
Item
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Title
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Chiral synthesis of ether-linked lipids via ring-opening of glycidyl derivatives mediated by boron trifluoride etherate.
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Identifier
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AAI9009737
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identifier
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9009737
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Creator
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Guivisdalsky, Pedro N.
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Contributor
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Adviser: Robert Bittman
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Date
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1989
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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 | Chemistry, Biochemistry | Chemistry, Pharmaceutical
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Abstract
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The boron trifluoride etherate mediated regio- and stereoselective nucleophilic opening of ({dollar}R{dollar})- and ({dollar}S{dollar})-glycidyl derivatives, such as the tosylate, {dollar}p{dollar}-nitrobenzenesulfonate, and oxiranemethanol {dollar}tert{dollar}-butyldiphenylsilyl ether is reported in this dissertation. The stereoselectivity of the ring-opening reaction with different nucleophiles such as benzyl alcohol, thiophenol, and various long-chain alcohols (1-hexadecanol, oleyl alcohol, and petroselenyl alcohol), was determined by chiral high-pressure liquid chromatography and high-field {dollar}\sp1{dollar}H-NMR spectroscopy of the ({dollar}R{dollar})-(+)-{dollar}\alpha{dollar}-trifluoromethylphenylacetic acid esters. The regioselectivity of the ring opening reaction (C{dollar}\sb3{dollar} vs. C{dollar}\sb1{dollar}) was studied by reverse-phase high-pressure liquid chromatography. When long-chain alcohols are used as the nucleophiles, the ring-opened product is converted into ether-linked phospho- and glycolipids of biological importance. The syntheses of 1-{dollar}O{dollar}-hexadecyl-2-acetyl-{dollar}sn{dollar}-3-glycerophosphocholine (platelet activating factor) and 1-O-hexadecyl-2-O-methyl-sn-3-glycerophosphocholine and their enantiomers 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.
