A Ready Conversion of a Pregnane-20-carboxaldehyde to 17α-Hydroxypregnan-20-ones and Pregn-16-en-20-ones
Reaction of (20S)‐5α‐chloro‐3β‐hydroxypregnane‐20‐carboxaldehyde (9, prepared in two steps from stigmasterol) with oxygen and potassium tert‐butoxide, followed by trimethyl phosphite treatment, afforded 5α‐chloro‐3β,17α‐dihydroxypregnan‐20‐one (6) and 3β,17α‐dihydroxypregn‐5‐en‐20‐one (7). This mixt...
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| Veröffentlicht in: | Liebigs Annalen der Chemie 1982, Vol.1982 (10), p.1829-1835 |
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| creator | Biancini, Bruno Caciagli, Valerio Centini, Felice Eletti-Bianchi, Giancarlo Re, Luciano |
| description | Reaction of (20S)‐5α‐chloro‐3β‐hydroxypregnane‐20‐carboxaldehyde (9, prepared in two steps from stigmasterol) with oxygen and potassium tert‐butoxide, followed by trimethyl phosphite treatment, afforded 5α‐chloro‐3β,17α‐dihydroxypregnan‐20‐one (6) and 3β,17α‐dihydroxypregn‐5‐en‐20‐one (7). This mixture was converted into 7 by potassium hydroxide treatment, and into 17α‐hydroxypregn‐4‐ene‐3,20‐dione (8) by reaction with pyridinium dichromate followed by potassium hydroxide treatment. Bromination‐dehydrobromination of 9, in one or two steps, afforded (Z)‐ and (E)‐5α‐chloro‐3β‐hydroxypregn‐17(20)‐ene‐20‐carboxaldehyde (11). Reaction of 11 with oxygen and potassium hydroxide gave 5α‐chloro‐3β‐hydroxypregn‐16‐en‐20‐one (12), which was converted to 3β‐hydroxypregna‐15,6‐dien‐20‐one (13) by further potassium hydroxide treatment, and to pregna‐4,16‐diene‐3,20‐dione (14) by Oppenauer reaction using excess aluminium isopropoxide.
Einfache Umwandlung eines Pregnan‐20‐carboxaldehyds in 17α‐Hydroxypregnan‐20‐one und Pregn‐16‐en‐20‐one
Umsetzung von (20S)‐5α‐Chlor‐3β‐hydroxypregnan‐20‐carboxaldehyd (9, dargestellt in zwei Stufen aus Stigmasterin) mit Sauerstoff und Kalium‐tert‐butylat sowie anschließend mit Trimethylphosphit lieferte 5α‐Chlor‐3β,17α‐dihydroxypregnan‐20‐on (6) und 3β, 17α‐Dihydroxypregn‐5‐en‐20‐on (7). Diese Mischung wurde durch Kaliumhydroxid in 7 übergeführt, während Reaktion mit Pyridinium‐dichromat und danach mit Kaliumhydroxid 17α‐Hydroxypregn‐4‐en‐3,20‐dion (8) ergab. Bromierung‐Dehydrobromierung von 9 in einer oder zwei Stufen ergab (Z)‐ und (E)‐5α‐Chlor‐3β‐hydroxypregn‐17(20)‐en‐20‐carboxaldehyd (11). Dessen Reaktion mit Sauerstoff und Kaliumhydroxid lieferte 5α‐Chlor‐3β‐hydroxypregn‐16‐en‐20‐on (12). Letzteres wurde durch weitere Kaliumhydroxid‐Behandlung in 3β‐Hydroxypregna‐5,16 dien‐20‐on (13) und mittels Oppenauer‐Reaktion, unter Anwendung von überschüssigem Aluminiumisopropylat, in Pregna‐4,16‐dien‐3,20‐dion (14) übergeführt. |
| doi_str_mv | 10.1002/jlac.198219821007 |
| format | Article |
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Einfache Umwandlung eines Pregnan‐20‐carboxaldehyds in 17α‐Hydroxypregnan‐20‐one und Pregn‐16‐en‐20‐one
Umsetzung von (20S)‐5α‐Chlor‐3β‐hydroxypregnan‐20‐carboxaldehyd (9, dargestellt in zwei Stufen aus Stigmasterin) mit Sauerstoff und Kalium‐tert‐butylat sowie anschließend mit Trimethylphosphit lieferte 5α‐Chlor‐3β,17α‐dihydroxypregnan‐20‐on (6) und 3β, 17α‐Dihydroxypregn‐5‐en‐20‐on (7). Diese Mischung wurde durch Kaliumhydroxid in 7 übergeführt, während Reaktion mit Pyridinium‐dichromat und danach mit Kaliumhydroxid 17α‐Hydroxypregn‐4‐en‐3,20‐dion (8) ergab. Bromierung‐Dehydrobromierung von 9 in einer oder zwei Stufen ergab (Z)‐ und (E)‐5α‐Chlor‐3β‐hydroxypregn‐17(20)‐en‐20‐carboxaldehyd (11). Dessen Reaktion mit Sauerstoff und Kaliumhydroxid lieferte 5α‐Chlor‐3β‐hydroxypregn‐16‐en‐20‐on (12). Letzteres wurde durch weitere Kaliumhydroxid‐Behandlung in 3β‐Hydroxypregna‐5,16 dien‐20‐on (13) und mittels Oppenauer‐Reaktion, unter Anwendung von überschüssigem Aluminiumisopropylat, in Pregna‐4,16‐dien‐3,20‐dion (14) übergeführt.</description><identifier>ISSN: 0170-2041</identifier><identifier>EISSN: 1099-0690</identifier><identifier>DOI: 10.1002/jlac.198219821007</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><ispartof>Liebigs Annalen der Chemie, 1982, Vol.1982 (10), p.1829-1835</ispartof><rights>Copyright © 1982 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3397-66ed371a408eff491588f852bae33f4ed3f93f0fb74e87ee62301da43ffb8db63</citedby><cites>FETCH-LOGICAL-c3397-66ed371a408eff491588f852bae33f4ed3f93f0fb74e87ee62301da43ffb8db63</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fjlac.198219821007$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fjlac.198219821007$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids></links><search><creatorcontrib>Biancini, Bruno</creatorcontrib><creatorcontrib>Caciagli, Valerio</creatorcontrib><creatorcontrib>Centini, Felice</creatorcontrib><creatorcontrib>Eletti-Bianchi, Giancarlo</creatorcontrib><creatorcontrib>Re, Luciano</creatorcontrib><title>A Ready Conversion of a Pregnane-20-carboxaldehyde to 17α-Hydroxypregnan-20-ones and Pregn-16-en-20-ones</title><title>Liebigs Annalen der Chemie</title><addtitle>Liebigs Ann. Chem</addtitle><description>Reaction of (20S)‐5α‐chloro‐3β‐hydroxypregnane‐20‐carboxaldehyde (9, prepared in two steps from stigmasterol) with oxygen and potassium tert‐butoxide, followed by trimethyl phosphite treatment, afforded 5α‐chloro‐3β,17α‐dihydroxypregnan‐20‐one (6) and 3β,17α‐dihydroxypregn‐5‐en‐20‐one (7). This mixture was converted into 7 by potassium hydroxide treatment, and into 17α‐hydroxypregn‐4‐ene‐3,20‐dione (8) by reaction with pyridinium dichromate followed by potassium hydroxide treatment. Bromination‐dehydrobromination of 9, in one or two steps, afforded (Z)‐ and (E)‐5α‐chloro‐3β‐hydroxypregn‐17(20)‐ene‐20‐carboxaldehyde (11). Reaction of 11 with oxygen and potassium hydroxide gave 5α‐chloro‐3β‐hydroxypregn‐16‐en‐20‐one (12), which was converted to 3β‐hydroxypregna‐15,6‐dien‐20‐one (13) by further potassium hydroxide treatment, and to pregna‐4,16‐diene‐3,20‐dione (14) by Oppenauer reaction using excess aluminium isopropoxide.
Einfache Umwandlung eines Pregnan‐20‐carboxaldehyds in 17α‐Hydroxypregnan‐20‐one und Pregn‐16‐en‐20‐one
Umsetzung von (20S)‐5α‐Chlor‐3β‐hydroxypregnan‐20‐carboxaldehyd (9, dargestellt in zwei Stufen aus Stigmasterin) mit Sauerstoff und Kalium‐tert‐butylat sowie anschließend mit Trimethylphosphit lieferte 5α‐Chlor‐3β,17α‐dihydroxypregnan‐20‐on (6) und 3β, 17α‐Dihydroxypregn‐5‐en‐20‐on (7). Diese Mischung wurde durch Kaliumhydroxid in 7 übergeführt, während Reaktion mit Pyridinium‐dichromat und danach mit Kaliumhydroxid 17α‐Hydroxypregn‐4‐en‐3,20‐dion (8) ergab. Bromierung‐Dehydrobromierung von 9 in einer oder zwei Stufen ergab (Z)‐ und (E)‐5α‐Chlor‐3β‐hydroxypregn‐17(20)‐en‐20‐carboxaldehyd (11). Dessen Reaktion mit Sauerstoff und Kaliumhydroxid lieferte 5α‐Chlor‐3β‐hydroxypregn‐16‐en‐20‐on (12). Letzteres wurde durch weitere Kaliumhydroxid‐Behandlung in 3β‐Hydroxypregna‐5,16 dien‐20‐on (13) und mittels Oppenauer‐Reaktion, unter Anwendung von überschüssigem Aluminiumisopropylat, in Pregna‐4,16‐dien‐3,20‐dion (14) übergeführt.</description><issn>0170-2041</issn><issn>1099-0690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1982</creationdate><recordtype>article</recordtype><recordid>eNqFkEFOwzAQRS0EEqVwAHa5gMs4duJkhaoIWmgFFQK6tJx4DCkhqewKmmNxEc5ES1CF2LAYjTTz31t8Qk4ZDBhAeLaodDFgaRJ-D4DcIz0GaUohTmGf9IBJoCEIdkiOvF8ACMGisEfKYXCH2rRB1tRv6HzZ1EFjAx3MHD7VusYNRAvt8matK4PPrcFg1QRMfn7QcWtcs26XXXIbbGr0ga5NR1MWU9zdj8mB1ZXHk5_dJw-XF_fZmE5vR1fZcEoLzlNJ4xgNl0wLSNBakbIoSWwShblGzq3YPG3KLdhcCkwkYhxyYEYLbm2emDzmfcI6b-Ea7x1atXTlq3atYqC2XaltV-p3VxvmvGPeywrb_wF1PR1mfwy0M5R-heudQbsXFUsuIzW_Ganx5FHMRzNQE_4FqJx-eg</recordid><startdate>1982</startdate><enddate>1982</enddate><creator>Biancini, Bruno</creator><creator>Caciagli, Valerio</creator><creator>Centini, Felice</creator><creator>Eletti-Bianchi, Giancarlo</creator><creator>Re, Luciano</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>1982</creationdate><title>A Ready Conversion of a Pregnane-20-carboxaldehyde to 17α-Hydroxypregnan-20-ones and Pregn-16-en-20-ones</title><author>Biancini, Bruno ; Caciagli, Valerio ; Centini, Felice ; Eletti-Bianchi, Giancarlo ; Re, Luciano</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3397-66ed371a408eff491588f852bae33f4ed3f93f0fb74e87ee62301da43ffb8db63</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1982</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Biancini, Bruno</creatorcontrib><creatorcontrib>Caciagli, Valerio</creatorcontrib><creatorcontrib>Centini, Felice</creatorcontrib><creatorcontrib>Eletti-Bianchi, Giancarlo</creatorcontrib><creatorcontrib>Re, Luciano</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Liebigs Annalen der Chemie</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Biancini, Bruno</au><au>Caciagli, Valerio</au><au>Centini, Felice</au><au>Eletti-Bianchi, Giancarlo</au><au>Re, Luciano</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Ready Conversion of a Pregnane-20-carboxaldehyde to 17α-Hydroxypregnan-20-ones and Pregn-16-en-20-ones</atitle><jtitle>Liebigs Annalen der Chemie</jtitle><addtitle>Liebigs Ann. Chem</addtitle><date>1982</date><risdate>1982</risdate><volume>1982</volume><issue>10</issue><spage>1829</spage><epage>1835</epage><pages>1829-1835</pages><issn>0170-2041</issn><eissn>1099-0690</eissn><abstract>Reaction of (20S)‐5α‐chloro‐3β‐hydroxypregnane‐20‐carboxaldehyde (9, prepared in two steps from stigmasterol) with oxygen and potassium tert‐butoxide, followed by trimethyl phosphite treatment, afforded 5α‐chloro‐3β,17α‐dihydroxypregnan‐20‐one (6) and 3β,17α‐dihydroxypregn‐5‐en‐20‐one (7). This mixture was converted into 7 by potassium hydroxide treatment, and into 17α‐hydroxypregn‐4‐ene‐3,20‐dione (8) by reaction with pyridinium dichromate followed by potassium hydroxide treatment. Bromination‐dehydrobromination of 9, in one or two steps, afforded (Z)‐ and (E)‐5α‐chloro‐3β‐hydroxypregn‐17(20)‐ene‐20‐carboxaldehyde (11). Reaction of 11 with oxygen and potassium hydroxide gave 5α‐chloro‐3β‐hydroxypregn‐16‐en‐20‐one (12), which was converted to 3β‐hydroxypregna‐15,6‐dien‐20‐one (13) by further potassium hydroxide treatment, and to pregna‐4,16‐diene‐3,20‐dione (14) by Oppenauer reaction using excess aluminium isopropoxide.
Einfache Umwandlung eines Pregnan‐20‐carboxaldehyds in 17α‐Hydroxypregnan‐20‐one und Pregn‐16‐en‐20‐one
Umsetzung von (20S)‐5α‐Chlor‐3β‐hydroxypregnan‐20‐carboxaldehyd (9, dargestellt in zwei Stufen aus Stigmasterin) mit Sauerstoff und Kalium‐tert‐butylat sowie anschließend mit Trimethylphosphit lieferte 5α‐Chlor‐3β,17α‐dihydroxypregnan‐20‐on (6) und 3β, 17α‐Dihydroxypregn‐5‐en‐20‐on (7). Diese Mischung wurde durch Kaliumhydroxid in 7 übergeführt, während Reaktion mit Pyridinium‐dichromat und danach mit Kaliumhydroxid 17α‐Hydroxypregn‐4‐en‐3,20‐dion (8) ergab. Bromierung‐Dehydrobromierung von 9 in einer oder zwei Stufen ergab (Z)‐ und (E)‐5α‐Chlor‐3β‐hydroxypregn‐17(20)‐en‐20‐carboxaldehyd (11). Dessen Reaktion mit Sauerstoff und Kaliumhydroxid lieferte 5α‐Chlor‐3β‐hydroxypregn‐16‐en‐20‐on (12). Letzteres wurde durch weitere Kaliumhydroxid‐Behandlung in 3β‐Hydroxypregna‐5,16 dien‐20‐on (13) und mittels Oppenauer‐Reaktion, unter Anwendung von überschüssigem Aluminiumisopropylat, in Pregna‐4,16‐dien‐3,20‐dion (14) übergeführt.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/jlac.198219821007</doi><tpages>7</tpages></addata></record> |
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| title | A Ready Conversion of a Pregnane-20-carboxaldehyde to 17α-Hydroxypregnan-20-ones and Pregn-16-en-20-ones |
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