Synthesis of Plasmalogen via 2,3-Bis-O-(4‘-methoxybenzyl)-sn-glycerol
The synthesis of the O-vinyl ether phospholipid plasmalogen 1 from 2,3-bis-O-[p-methoxybenzyl (PMB)]-sn-glycerol (13) is described. Treatment of 13 with potassium hydride, trichloroethylene, and n-butyllithium gave a 1-O-alkynyl glycerol derivative, which was alkylated with 1-iodohexadecane to affor...
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| Veröffentlicht in: | Journal of the American Chemical Society 1999-02, Vol.121 (4), p.662-668 |
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| creator | Qin, Donghui Byun, Hoe-Sup Bittman, Robert |
| description | The synthesis of the O-vinyl ether phospholipid plasmalogen 1 from 2,3-bis-O-[p-methoxybenzyl (PMB)]-sn-glycerol (13) is described. Treatment of 13 with potassium hydride, trichloroethylene, and n-butyllithium gave a 1-O-alkynyl glycerol derivative, which was alkylated with 1-iodohexadecane to afford the long-chain O-alkynyl ether 14. The latter was quantitatively converted to cis-enol ether 15 (Z/E ratio between 35:1 and 100:1) with Lindlar catalyst in hexane/EtOAc 1:1 containing quinoline. The PMB groups of 15 were removed by Birch reduction (Na, NH3), giving 1-O-[1‘-(Z)-octadecenyl]-sn-glycerol (2) in 95% yield. Regioselective silylation of 2 followed by palmitoylation provided 1-O-[1‘-(Z)-octadecenyl]-2-O-palmitoyl-3-(tert-butyldiphenylsilyl)-sn-glycerol (17). Desilylation with Bu4NF/imidazole at −23 °C followed by phosphocholine insertion (using 2-chloro-2-oxo-1,3,2-dioxaphospholane with 2 equiv of pyridine in benzene at 4 °C and then trimethylamine in benzene/MeCN 1:3 at 70 °C) completes the synthesis of plasmalogen (1). |
| doi_str_mv | 10.1021/ja982837o |
| format | Article |
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Treatment of 13 with potassium hydride, trichloroethylene, and n-butyllithium gave a 1-O-alkynyl glycerol derivative, which was alkylated with 1-iodohexadecane to afford the long-chain O-alkynyl ether 14. The latter was quantitatively converted to cis-enol ether 15 (Z/E ratio between 35:1 and 100:1) with Lindlar catalyst in hexane/EtOAc 1:1 containing quinoline. The PMB groups of 15 were removed by Birch reduction (Na, NH3), giving 1-O-[1‘-(Z)-octadecenyl]-sn-glycerol (2) in 95% yield. Regioselective silylation of 2 followed by palmitoylation provided 1-O-[1‘-(Z)-octadecenyl]-2-O-palmitoyl-3-(tert-butyldiphenylsilyl)-sn-glycerol (17). Desilylation with Bu4NF/imidazole at −23 °C followed by phosphocholine insertion (using 2-chloro-2-oxo-1,3,2-dioxaphospholane with 2 equiv of pyridine in benzene at 4 °C and then trimethylamine in benzene/MeCN 1:3 at 70 °C) completes the synthesis of plasmalogen (1).</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja982837o</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 1999-02, Vol.121 (4), p.662-668</ispartof><rights>Copyright © 1999 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a361t-c1788e2f3d56fe0c3c321afa8a38bfe39688ac969a5aa8feca898711d0a5df883</citedby><cites>FETCH-LOGICAL-a361t-c1788e2f3d56fe0c3c321afa8a38bfe39688ac969a5aa8feca898711d0a5df883</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja982837o$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja982837o$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids></links><search><creatorcontrib>Qin, Donghui</creatorcontrib><creatorcontrib>Byun, Hoe-Sup</creatorcontrib><creatorcontrib>Bittman, Robert</creatorcontrib><title>Synthesis of Plasmalogen via 2,3-Bis-O-(4‘-methoxybenzyl)-sn-glycerol</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>The synthesis of the O-vinyl ether phospholipid plasmalogen 1 from 2,3-bis-O-[p-methoxybenzyl (PMB)]-sn-glycerol (13) is described. Treatment of 13 with potassium hydride, trichloroethylene, and n-butyllithium gave a 1-O-alkynyl glycerol derivative, which was alkylated with 1-iodohexadecane to afford the long-chain O-alkynyl ether 14. The latter was quantitatively converted to cis-enol ether 15 (Z/E ratio between 35:1 and 100:1) with Lindlar catalyst in hexane/EtOAc 1:1 containing quinoline. The PMB groups of 15 were removed by Birch reduction (Na, NH3), giving 1-O-[1‘-(Z)-octadecenyl]-sn-glycerol (2) in 95% yield. Regioselective silylation of 2 followed by palmitoylation provided 1-O-[1‘-(Z)-octadecenyl]-2-O-palmitoyl-3-(tert-butyldiphenylsilyl)-sn-glycerol (17). Desilylation with Bu4NF/imidazole at −23 °C followed by phosphocholine insertion (using 2-chloro-2-oxo-1,3,2-dioxaphospholane with 2 equiv of pyridine in benzene at 4 °C and then trimethylamine in benzene/MeCN 1:3 at 70 °C) completes the synthesis of plasmalogen (1).</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><recordid>eNpt0M1Kw0AUBeBBFKzVhW-QjWDB0flpJjdLrTYKlRZbwd1wO51pU9OkZKI0rnwMn88nMVLpytXlwseBcwg55eySM8GvlhiDABkVe6TFQ8FoyIXaJy3GmKARKHlIjrxfNm9XAG-RZFzn1cL61AeFC0YZ-hVmxdzmwXuKgbiQ9Cb1dEjPu9-fX3Rlq0Wxqac2_6izDvU5nWe1sWWRHZMDh5m3J3-3TZ77d5PePR0Mk4fe9YCiVLyihkcAVjg5C5WzzEgjBUeHgBKmzspYAaCJVYwhIjhrEGKIOJ8xDGcOQLZJZ5trysL70jq9LtMVlrXmTP8uoHcLNJZubeoru9lBLF-1imQU6slorG9fnhI-6D_qpPFnW4_G62XxVuZNk39yfwAK32oQ</recordid><startdate>19990203</startdate><enddate>19990203</enddate><creator>Qin, Donghui</creator><creator>Byun, Hoe-Sup</creator><creator>Bittman, Robert</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19990203</creationdate><title>Synthesis of Plasmalogen via 2,3-Bis-O-(4‘-methoxybenzyl)-sn-glycerol</title><author>Qin, Donghui ; Byun, Hoe-Sup ; Bittman, Robert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a361t-c1788e2f3d56fe0c3c321afa8a38bfe39688ac969a5aa8feca898711d0a5df883</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1999</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Qin, Donghui</creatorcontrib><creatorcontrib>Byun, Hoe-Sup</creatorcontrib><creatorcontrib>Bittman, Robert</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Qin, Donghui</au><au>Byun, Hoe-Sup</au><au>Bittman, Robert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of Plasmalogen via 2,3-Bis-O-(4‘-methoxybenzyl)-sn-glycerol</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1999-02-03</date><risdate>1999</risdate><volume>121</volume><issue>4</issue><spage>662</spage><epage>668</epage><pages>662-668</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The synthesis of the O-vinyl ether phospholipid plasmalogen 1 from 2,3-bis-O-[p-methoxybenzyl (PMB)]-sn-glycerol (13) is described. Treatment of 13 with potassium hydride, trichloroethylene, and n-butyllithium gave a 1-O-alkynyl glycerol derivative, which was alkylated with 1-iodohexadecane to afford the long-chain O-alkynyl ether 14. The latter was quantitatively converted to cis-enol ether 15 (Z/E ratio between 35:1 and 100:1) with Lindlar catalyst in hexane/EtOAc 1:1 containing quinoline. The PMB groups of 15 were removed by Birch reduction (Na, NH3), giving 1-O-[1‘-(Z)-octadecenyl]-sn-glycerol (2) in 95% yield. Regioselective silylation of 2 followed by palmitoylation provided 1-O-[1‘-(Z)-octadecenyl]-2-O-palmitoyl-3-(tert-butyldiphenylsilyl)-sn-glycerol (17). Desilylation with Bu4NF/imidazole at −23 °C followed by phosphocholine insertion (using 2-chloro-2-oxo-1,3,2-dioxaphospholane with 2 equiv of pyridine in benzene at 4 °C and then trimethylamine in benzene/MeCN 1:3 at 70 °C) completes the synthesis of plasmalogen (1).</abstract><pub>American Chemical Society</pub><doi>10.1021/ja982837o</doi><tpages>7</tpages></addata></record> |
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| title | Synthesis of Plasmalogen via 2,3-Bis-O-(4‘-methoxybenzyl)-sn-glycerol |
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