| Lyso platelet activating factor (LysoPAF) and its enantiomer. Total synthesis and carbon-13 NMR spectroscopy. | |
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MedLine Citation:
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PMID: 2079867 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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Described is a reaction sequence for the total synthesis of lyso platelet activating factor (lysoPAF; 1-O-alkyl-sn-glycero-3-phosphocholine) and its enantiomer. The procedure is versatile and yields optically pure isomers of defined chain length. The synthesis is equally suited for the preparation of lysoPAF analogues and its enantiomers with unsaturation in the long aliphatic chain. First, rac-1(3)-O-alkylglycerol is prepared by alkylation of rac-isopropylideneglycerol with alkyl methanesulfonate followed by acid-catalyzed removal of the ketal group. The primary hydroxy group of alkylglycerol is then protected by tritylation, the secondary hydroxy group is acylated, and the protective trityl group is removed under mild acidic conditions with boric acid on silicic acid, essentially without acyl migration. Condensation of the diradylglycerol with bromoethyl dichlorophosphate in diethyl ether, hydrolysis of the resulting chloride, and nucleophilic displacement of the bromine with trimethylamine gives rac-1-O-alkyl-2-acylglycero-3-phosphocholine in good overall yield. The racemic alkylacylglycerophosphocholine is finally treated with snake venom phospholipase A2 (Ophiophagus hannah) which affords 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) of natural configuration in optically pure form. The "unnatural" 3-O-alkyl-2-O-acyl-sn-glycero-1-phosphocholine enantiomer, which is not susceptible to phospholipase A2 cleavage, gives 3-O-alkyl-sn-glycero-1-phosphocholine upon deacylation with methanolic sodium hydroxide. Homogeneity and structure of the intermediates and final products were ascertained by carbon-13 nuclear magnetic resonance spectroscopy on monomeric solutions. |
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Authors:
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M P Murari; R Murari; S Parthasarathy; C A Guy; V V Kumar; B Malewicz; W J Baumann |
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Publication Detail:
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Type: Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, P.H.S. |
Journal Detail:
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Title: Lipids Volume: 25 ISSN: 0024-4201 ISO Abbreviation: Lipids Publication Date: 1990 Oct |
Date Detail:
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Created Date: 1991-04-26 Completed Date: 1991-04-26 Revised Date: 2008-11-21 |
Medline Journal Info:
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Nlm Unique ID: 0060450 Medline TA: Lipids Country: UNITED STATES |
Other Details:
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Languages: eng Pagination: 606-12 Citation Subset: IM |
Affiliation:
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Section of Bio-Organic Chemistry, Hormel Institute, University of Minnesota, Austin 55912. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Acylation Alkylation Chemical Phenomena Chemistry Magnetic Resonance Spectroscopy Molecular Structure Platelet Activating Factor / analogs & derivatives*, chemical synthesis, chemistry Stereoisomerism |
| Grant Support | |
ID/Acronym/Agency:
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HL07311/HL/NHLBI NIH HHS; HL08214/HL/NHLBI NIH HHS; RR 04654/RR/NCRR NIH HHS |
| Chemical | |
Reg. No./Substance:
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0/O-deacetyl platelet activating factor; 0/Platelet Activating Factor |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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