Potential Bile Acid Metabolites. 25. Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16- and 3α,7α,15-Trihydroxy-5β-cholan-24-oic Acids
Epimeric 3α,7α,16- and 3α,7α,15-trihydroxy-5β-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA...
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| Veröffentlicht in: | Chemical & pharmaceutical bulletin 2002, Vol.50(10), pp.1327-1334 |
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| creator | Iida, Takashi Hikosaka, Masahiro Kakiyama, Genta Shiraishi, Keisuke Schteingart, Claudio D. Hagey, Lee R. Ton-Nu, Huong-Thu Hofmann, Alan F. Mano, Nariyasu Goto, Junichi Nambara, Toshio |
| description | Epimeric 3α,7α,16- and 3α,7α,15-trihydroxy-5β-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17α- and 14α-hydroxy derivatives with POCl3 or conc. H2SO4, the respective Δ16- and Δ14-unsaturated products were subjected to hydration via hydroboration followed by oxidation to yield the 3,7,16- and 3,7,15-triketones, respectively. Stereoselective reduction of the respective triketones with tert-butylamine-borane complex afforded the epimeric 3α,7α,16- or 3α,7α,15-trihydroxy derivatives exclusively. A facile formation of the corresponding ε-lactones between the side chain carboxyl group at C-24 and the 16α- (or 16β-) hydroxyl group in bile acids is also clarified. |
| doi_str_mv | 10.1248/cpb.50.1327 |
| format | Article |
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Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16- and 3α,7α,15-Trihydroxy-5β-cholan-24-oic Acids</title><source>J-STAGE Free</source><source>EZB-FREE-00999 freely available EZB journals</source><source>Free Full-Text Journals in Chemistry</source><creator>Iida, Takashi ; Hikosaka, Masahiro ; Kakiyama, Genta ; Shiraishi, Keisuke ; Schteingart, Claudio D. ; Hagey, Lee R. ; Ton-Nu, Huong-Thu ; Hofmann, Alan F. ; Mano, Nariyasu ; Goto, Junichi ; Nambara, Toshio</creator><creatorcontrib>Iida, Takashi ; Hikosaka, Masahiro ; Kakiyama, Genta ; Shiraishi, Keisuke ; Schteingart, Claudio D. ; Hagey, Lee R. ; Ton-Nu, Huong-Thu ; Hofmann, Alan F. ; Mano, Nariyasu ; Goto, Junichi ; Nambara, Toshio</creatorcontrib><description>Epimeric 3α,7α,16- and 3α,7α,15-trihydroxy-5β-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17α- and 14α-hydroxy derivatives with POCl3 or conc. H2SO4, the respective Δ16- and Δ14-unsaturated products were subjected to hydration via hydroboration followed by oxidation to yield the 3,7,16- and 3,7,15-triketones, respectively. Stereoselective reduction of the respective triketones with tert-butylamine-borane complex afforded the epimeric 3α,7α,16- or 3α,7α,15-trihydroxy derivatives exclusively. A facile formation of the corresponding ε-lactones between the side chain carboxyl group at C-24 and the 16α- (or 16β-) hydroxyl group in bile acids is also clarified.</description><identifier>ISSN: 0009-2363</identifier><identifier>EISSN: 1347-5223</identifier><identifier>DOI: 10.1248/cpb.50.1327</identifier><identifier>CODEN: CPBTAL</identifier><language>eng</language><publisher>Tokyo: The Pharmaceutical Society of Japan</publisher><subject>3α,7α,15-trihydroxy-5β-cholan-24-oic acid ; 3α,7α,16-trihydroxy-5β-cholan-24-oic acid ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Chemistry ; dimethyldioxirane ; Exact sciences and technology ; Organic chemistry ; Preparations and properties ; remote oxyfunctionalization ; Steroids ; ε-lactone</subject><ispartof>Chemical and Pharmaceutical Bulletin, 2002, Vol.50(10), pp.1327-1334</ispartof><rights>2002 The Pharmaceutical Society of Japan</rights><rights>2003 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,1883,27924,27925</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=13996174$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Iida, Takashi</creatorcontrib><creatorcontrib>Hikosaka, Masahiro</creatorcontrib><creatorcontrib>Kakiyama, Genta</creatorcontrib><creatorcontrib>Shiraishi, Keisuke</creatorcontrib><creatorcontrib>Schteingart, Claudio D.</creatorcontrib><creatorcontrib>Hagey, Lee R.</creatorcontrib><creatorcontrib>Ton-Nu, Huong-Thu</creatorcontrib><creatorcontrib>Hofmann, Alan F.</creatorcontrib><creatorcontrib>Mano, Nariyasu</creatorcontrib><creatorcontrib>Goto, Junichi</creatorcontrib><creatorcontrib>Nambara, Toshio</creatorcontrib><title>Potential Bile Acid Metabolites. 25. Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16- and 3α,7α,15-Trihydroxy-5β-cholan-24-oic Acids</title><title>Chemical & pharmaceutical bulletin</title><addtitle>Chem. Pharm. Bull.</addtitle><description>Epimeric 3α,7α,16- and 3α,7α,15-trihydroxy-5β-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17α- and 14α-hydroxy derivatives with POCl3 or conc. H2SO4, the respective Δ16- and Δ14-unsaturated products were subjected to hydration via hydroboration followed by oxidation to yield the 3,7,16- and 3,7,15-triketones, respectively. Stereoselective reduction of the respective triketones with tert-butylamine-borane complex afforded the epimeric 3α,7α,16- or 3α,7α,15-trihydroxy derivatives exclusively. A facile formation of the corresponding ε-lactones between the side chain carboxyl group at C-24 and the 16α- (or 16β-) hydroxyl group in bile acids is also clarified.</description><subject>3α,7α,15-trihydroxy-5β-cholan-24-oic acid</subject><subject>3α,7α,16-trihydroxy-5β-cholan-24-oic acid</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Chemistry</subject><subject>dimethyldioxirane</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>remote oxyfunctionalization</subject><subject>Steroids</subject><subject>ε-lactone</subject><issn>0009-2363</issn><issn>1347-5223</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><recordid>eNpFUUtOwzAQtRBIlMKKC3jDDhfbY8fNEip-EgiklnVkOw5xlcaV7QW9CPeAg_RMpIBgMT_Ne6N5MwidMjphXEwv7NpM5JADV3toxEAoIjmHfTSilJaEQwGH6CilJaVcUgUj9P4csuuz1x2-8p3Dl9bX-NFlbULns0sTzOUEzzd9bl3yCeu-xrPWrbwdGM8xrF3M3iUcGjzPLrrgU1i56C2G7ce5GowV5Jv1V0uyiL7d1DG8bYjcfhLbhk73hAsSBt5ug3SMDhrdJXfyG8fo5eZ6MbsjD0-397PLB7LkQmUChtnCymnNQbKSKwZGMsFUY0qQthRaCCinjJtCqYIKBs4yoYxRYEADozBGZz9z1zoNipqoe-tTtY5-peOmYlCWBVNiwF394JYp61f3B9CDetu5ajh8JWnF6K_ffeC_2epYuR6-AHPRgL8</recordid><startdate>200210</startdate><enddate>200210</enddate><creator>Iida, Takashi</creator><creator>Hikosaka, Masahiro</creator><creator>Kakiyama, Genta</creator><creator>Shiraishi, Keisuke</creator><creator>Schteingart, Claudio D.</creator><creator>Hagey, Lee R.</creator><creator>Ton-Nu, Huong-Thu</creator><creator>Hofmann, Alan F.</creator><creator>Mano, Nariyasu</creator><creator>Goto, Junichi</creator><creator>Nambara, Toshio</creator><general>The Pharmaceutical Society of Japan</general><general>Maruzen</general><scope>IQODW</scope></search><sort><creationdate>200210</creationdate><title>Potential Bile Acid Metabolites. 25. Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16- and 3α,7α,15-Trihydroxy-5β-cholan-24-oic Acids</title><author>Iida, Takashi ; Hikosaka, Masahiro ; Kakiyama, Genta ; Shiraishi, Keisuke ; Schteingart, Claudio D. ; Hagey, Lee R. ; Ton-Nu, Huong-Thu ; Hofmann, Alan F. ; Mano, Nariyasu ; Goto, Junichi ; Nambara, Toshio</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-j247t-3b1c6c58d235192713b51417fb935c94a4439812b67760413ec147bb73b3a3103</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>3α,7α,15-trihydroxy-5β-cholan-24-oic acid</topic><topic>3α,7α,16-trihydroxy-5β-cholan-24-oic acid</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Chemistry</topic><topic>dimethyldioxirane</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>remote oxyfunctionalization</topic><topic>Steroids</topic><topic>ε-lactone</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Iida, Takashi</creatorcontrib><creatorcontrib>Hikosaka, Masahiro</creatorcontrib><creatorcontrib>Kakiyama, Genta</creatorcontrib><creatorcontrib>Shiraishi, Keisuke</creatorcontrib><creatorcontrib>Schteingart, Claudio D.</creatorcontrib><creatorcontrib>Hagey, Lee R.</creatorcontrib><creatorcontrib>Ton-Nu, Huong-Thu</creatorcontrib><creatorcontrib>Hofmann, Alan F.</creatorcontrib><creatorcontrib>Mano, Nariyasu</creatorcontrib><creatorcontrib>Goto, Junichi</creatorcontrib><creatorcontrib>Nambara, Toshio</creatorcontrib><collection>Pascal-Francis</collection><jtitle>Chemical & pharmaceutical bulletin</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Iida, Takashi</au><au>Hikosaka, Masahiro</au><au>Kakiyama, Genta</au><au>Shiraishi, Keisuke</au><au>Schteingart, Claudio D.</au><au>Hagey, Lee R.</au><au>Ton-Nu, Huong-Thu</au><au>Hofmann, Alan F.</au><au>Mano, Nariyasu</au><au>Goto, Junichi</au><au>Nambara, Toshio</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Potential Bile Acid Metabolites. 25. Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16- and 3α,7α,15-Trihydroxy-5β-cholan-24-oic Acids</atitle><jtitle>Chemical & pharmaceutical bulletin</jtitle><addtitle>Chem. Pharm. Bull.</addtitle><date>2002-10</date><risdate>2002</risdate><volume>50</volume><issue>10</issue><spage>1327</spage><epage>1334</epage><pages>1327-1334</pages><issn>0009-2363</issn><eissn>1347-5223</eissn><coden>CPBTAL</coden><abstract>Epimeric 3α,7α,16- and 3α,7α,15-trihydroxy-5β-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17α- and 14α-hydroxy derivatives with POCl3 or conc. H2SO4, the respective Δ16- and Δ14-unsaturated products were subjected to hydration via hydroboration followed by oxidation to yield the 3,7,16- and 3,7,15-triketones, respectively. Stereoselective reduction of the respective triketones with tert-butylamine-borane complex afforded the epimeric 3α,7α,16- or 3α,7α,15-trihydroxy derivatives exclusively. A facile formation of the corresponding ε-lactones between the side chain carboxyl group at C-24 and the 16α- (or 16β-) hydroxyl group in bile acids is also clarified.</abstract><cop>Tokyo</cop><pub>The Pharmaceutical Society of Japan</pub><doi>10.1248/cpb.50.1327</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | 3α,7α,15-trihydroxy-5β-cholan-24-oic acid 3α,7α,16-trihydroxy-5β-cholan-24-oic acid Alicyclic compounds, terpenoids, prostaglandins, steroids Chemistry dimethyldioxirane Exact sciences and technology Organic chemistry Preparations and properties remote oxyfunctionalization Steroids ε-lactone |
| title | Potential Bile Acid Metabolites. 25. Synthesis and Chemical Properties of Stereoisomeric 3α,7α,16- and 3α,7α,15-Trihydroxy-5β-cholan-24-oic Acids |
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