Synthesis of the marine epoxy sterol 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol
The synthesis of 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol (1), a highly oxygenated marine sterol containing a 9,11-epoxide moiety in the nucleus, is described. Epoxy sterol 1 was synthesized from cholesta-5,7-dien-3 beta-ol. Oxidation of this sterol with m-chloroperbenzoic...
Gespeichert in:
| Veröffentlicht in: | Steroids 1991-03, Vol.56 (3), p.154-158 |
|---|---|
| Hauptverfasser: | , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 158 |
|---|---|
| container_issue | 3 |
| container_start_page | 154 |
| container_title | Steroids |
| container_volume | 56 |
| creator | Migliuolo, A Notaro, G Piccialli, V Sica, D |
| description | The synthesis of 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol (1), a highly oxygenated marine sterol containing a 9,11-epoxide moiety in the nucleus, is described. Epoxy sterol 1 was synthesized from cholesta-5,7-dien-3 beta-ol. Oxidation of this sterol with m-chloroperbenzoic acid followed by hydrolysis and acetylation furnished 5 alpha-cholest-7-ene-3 beta,5,6 alpha-triol 3,6-diacetate (2). Mercuric acetate dehydrogenation of diacetate 2, followed by oxidation with manganese dioxide and epoxidation with m-chloroper-benzoic acid, afforded 9 alpha,11 alpha-epoxy-3 beta,5-dihydroxy-5 alpha-cholest-7-en-6-one (5). Reduction of 5 with lithium aluminum hydride gave the desired compound 1. The structures of all synthetic intermediates were confirmed by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. A reassignment of resonances for carbons 1, 8, and 15 in the 13C NMR spectrum of 1, based on 2D-NMR correlation spectroscopy, has been accomplished. |
| doi_str_mv | 10.1016/0039-128X(91)90066-5 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_proquest_miscellaneous_80595513</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>80595513</sourcerecordid><originalsourceid>FETCH-LOGICAL-p138t-4bb63aab4d5405b1a5e4783db19fb3b7022ea1a6b90ee4acad24477ed1ebf20b3</originalsourceid><addsrcrecordid>eNo9kE1Lw0AQhveg1Fr9Bwp7EoWu7meSPUrxCwoeVPAWZpOJiWyzMZuC_feGNniaZ-Z9Gd4ZQi4EvxVcJHecK8uEzD6vrbixnCcJM0dk_j8-IacxfvNRUFbOyExyLaVSc_L1tmuHGmMTaajoSHQDfdMixS787mgcsA-eWgq-q2EpxAHYXmVm6oo6eIwDSxm2yBR1OMDSLJM9sKFvgj8jxxX4iOdTXZCPx4f31TNbvz69rO7XrBMqG5h2LlEATpdGc-MEGNRppkonbOWUS7mUCAISZzmihgJKqXWaYinQVZI7tSBXh71dH362Y6h808QCvYcWwzbmGTfWGKFG4-Vk3LoNlnnXN-Plu3z6jPoDiU9jpg</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>80595513</pqid></control><display><type>article</type><title>Synthesis of the marine epoxy sterol 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol</title><source>MEDLINE</source><source>Elsevier ScienceDirect Journals Complete</source><creator>Migliuolo, A ; Notaro, G ; Piccialli, V ; Sica, D</creator><creatorcontrib>Migliuolo, A ; Notaro, G ; Piccialli, V ; Sica, D</creatorcontrib><description>The synthesis of 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol (1), a highly oxygenated marine sterol containing a 9,11-epoxide moiety in the nucleus, is described. Epoxy sterol 1 was synthesized from cholesta-5,7-dien-3 beta-ol. Oxidation of this sterol with m-chloroperbenzoic acid followed by hydrolysis and acetylation furnished 5 alpha-cholest-7-ene-3 beta,5,6 alpha-triol 3,6-diacetate (2). Mercuric acetate dehydrogenation of diacetate 2, followed by oxidation with manganese dioxide and epoxidation with m-chloroper-benzoic acid, afforded 9 alpha,11 alpha-epoxy-3 beta,5-dihydroxy-5 alpha-cholest-7-en-6-one (5). Reduction of 5 with lithium aluminum hydride gave the desired compound 1. The structures of all synthetic intermediates were confirmed by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. A reassignment of resonances for carbons 1, 8, and 15 in the 13C NMR spectrum of 1, based on 2D-NMR correlation spectroscopy, has been accomplished.</description><identifier>ISSN: 0039-128X</identifier><identifier>DOI: 10.1016/0039-128X(91)90066-5</identifier><identifier>PMID: 2042233</identifier><language>eng</language><publisher>United States</publisher><subject>Acetylation ; Aluminum ; Aluminum Compounds ; Chlorobenzoates ; Cholestenes - chemical synthesis ; Cholestenes - chemistry ; Hydrolysis ; Lithium ; Lithium Compounds ; Magnetic Resonance Spectroscopy ; Manganese ; Manganese Compounds ; Mercury ; Molecular Structure ; Oxidation-Reduction ; Oxides</subject><ispartof>Steroids, 1991-03, Vol.56 (3), p.154-158</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/2042233$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Migliuolo, A</creatorcontrib><creatorcontrib>Notaro, G</creatorcontrib><creatorcontrib>Piccialli, V</creatorcontrib><creatorcontrib>Sica, D</creatorcontrib><title>Synthesis of the marine epoxy sterol 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol</title><title>Steroids</title><addtitle>Steroids</addtitle><description>The synthesis of 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol (1), a highly oxygenated marine sterol containing a 9,11-epoxide moiety in the nucleus, is described. Epoxy sterol 1 was synthesized from cholesta-5,7-dien-3 beta-ol. Oxidation of this sterol with m-chloroperbenzoic acid followed by hydrolysis and acetylation furnished 5 alpha-cholest-7-ene-3 beta,5,6 alpha-triol 3,6-diacetate (2). Mercuric acetate dehydrogenation of diacetate 2, followed by oxidation with manganese dioxide and epoxidation with m-chloroper-benzoic acid, afforded 9 alpha,11 alpha-epoxy-3 beta,5-dihydroxy-5 alpha-cholest-7-en-6-one (5). Reduction of 5 with lithium aluminum hydride gave the desired compound 1. The structures of all synthetic intermediates were confirmed by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. A reassignment of resonances for carbons 1, 8, and 15 in the 13C NMR spectrum of 1, based on 2D-NMR correlation spectroscopy, has been accomplished.</description><subject>Acetylation</subject><subject>Aluminum</subject><subject>Aluminum Compounds</subject><subject>Chlorobenzoates</subject><subject>Cholestenes - chemical synthesis</subject><subject>Cholestenes - chemistry</subject><subject>Hydrolysis</subject><subject>Lithium</subject><subject>Lithium Compounds</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Manganese</subject><subject>Manganese Compounds</subject><subject>Mercury</subject><subject>Molecular Structure</subject><subject>Oxidation-Reduction</subject><subject>Oxides</subject><issn>0039-128X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1991</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNo9kE1Lw0AQhveg1Fr9Bwp7EoWu7meSPUrxCwoeVPAWZpOJiWyzMZuC_feGNniaZ-Z9Gd4ZQi4EvxVcJHecK8uEzD6vrbixnCcJM0dk_j8-IacxfvNRUFbOyExyLaVSc_L1tmuHGmMTaajoSHQDfdMixS787mgcsA-eWgq-q2EpxAHYXmVm6oo6eIwDSxm2yBR1OMDSLJM9sKFvgj8jxxX4iOdTXZCPx4f31TNbvz69rO7XrBMqG5h2LlEATpdGc-MEGNRppkonbOWUS7mUCAISZzmihgJKqXWaYinQVZI7tSBXh71dH362Y6h808QCvYcWwzbmGTfWGKFG4-Vk3LoNlnnXN-Plu3z6jPoDiU9jpg</recordid><startdate>199103</startdate><enddate>199103</enddate><creator>Migliuolo, A</creator><creator>Notaro, G</creator><creator>Piccialli, V</creator><creator>Sica, D</creator><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>199103</creationdate><title>Synthesis of the marine epoxy sterol 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol</title><author>Migliuolo, A ; Notaro, G ; Piccialli, V ; Sica, D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p138t-4bb63aab4d5405b1a5e4783db19fb3b7022ea1a6b90ee4acad24477ed1ebf20b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1991</creationdate><topic>Acetylation</topic><topic>Aluminum</topic><topic>Aluminum Compounds</topic><topic>Chlorobenzoates</topic><topic>Cholestenes - chemical synthesis</topic><topic>Cholestenes - chemistry</topic><topic>Hydrolysis</topic><topic>Lithium</topic><topic>Lithium Compounds</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Manganese</topic><topic>Manganese Compounds</topic><topic>Mercury</topic><topic>Molecular Structure</topic><topic>Oxidation-Reduction</topic><topic>Oxides</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Migliuolo, A</creatorcontrib><creatorcontrib>Notaro, G</creatorcontrib><creatorcontrib>Piccialli, V</creatorcontrib><creatorcontrib>Sica, D</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Steroids</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Migliuolo, A</au><au>Notaro, G</au><au>Piccialli, V</au><au>Sica, D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of the marine epoxy sterol 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol</atitle><jtitle>Steroids</jtitle><addtitle>Steroids</addtitle><date>1991-03</date><risdate>1991</risdate><volume>56</volume><issue>3</issue><spage>154</spage><epage>158</epage><pages>154-158</pages><issn>0039-128X</issn><abstract>The synthesis of 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol (1), a highly oxygenated marine sterol containing a 9,11-epoxide moiety in the nucleus, is described. Epoxy sterol 1 was synthesized from cholesta-5,7-dien-3 beta-ol. Oxidation of this sterol with m-chloroperbenzoic acid followed by hydrolysis and acetylation furnished 5 alpha-cholest-7-ene-3 beta,5,6 alpha-triol 3,6-diacetate (2). Mercuric acetate dehydrogenation of diacetate 2, followed by oxidation with manganese dioxide and epoxidation with m-chloroper-benzoic acid, afforded 9 alpha,11 alpha-epoxy-3 beta,5-dihydroxy-5 alpha-cholest-7-en-6-one (5). Reduction of 5 with lithium aluminum hydride gave the desired compound 1. The structures of all synthetic intermediates were confirmed by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. A reassignment of resonances for carbons 1, 8, and 15 in the 13C NMR spectrum of 1, based on 2D-NMR correlation spectroscopy, has been accomplished.</abstract><cop>United States</cop><pmid>2042233</pmid><doi>10.1016/0039-128X(91)90066-5</doi><tpages>5</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0039-128X |
| ispartof | Steroids, 1991-03, Vol.56 (3), p.154-158 |
| issn | 0039-128X |
| language | eng |
| recordid | cdi_proquest_miscellaneous_80595513 |
| source | MEDLINE; Elsevier ScienceDirect Journals Complete |
| subjects | Acetylation Aluminum Aluminum Compounds Chlorobenzoates Cholestenes - chemical synthesis Cholestenes - chemistry Hydrolysis Lithium Lithium Compounds Magnetic Resonance Spectroscopy Manganese Manganese Compounds Mercury Molecular Structure Oxidation-Reduction Oxides |
| title | Synthesis of the marine epoxy sterol 9 alpha,11 alpha-epoxy-5 alpha-cholest-7-ene-3 beta,5,6 beta-triol |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-05T06%3A26%3A55IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Synthesis%20of%20the%20marine%20epoxy%20sterol%209%20alpha,11%20alpha-epoxy-5%20alpha-cholest-7-ene-3%20beta,5,6%20beta-triol&rft.jtitle=Steroids&rft.au=Migliuolo,%20A&rft.date=1991-03&rft.volume=56&rft.issue=3&rft.spage=154&rft.epage=158&rft.pages=154-158&rft.issn=0039-128X&rft_id=info:doi/10.1016/0039-128X(91)90066-5&rft_dat=%3Cproquest_pubme%3E80595513%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=80595513&rft_id=info:pmid/2042233&rfr_iscdi=true |