Synthesis of 1α-Hydroxyvitamin D5 Using a Modified Two Wavelength Photolysis for Vitamin D Formation
1α-Hydroxyvitamin D5 (1) is a promising chemopreventive agent for breast cancer and is being developed as a drug. We report a synthesis for this vitamin D analogue which uses a photochemical method for the B-ring opening, leading to the conjugated triene system. The precursor 7-dehydrositosteryl ace...
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| Veröffentlicht in: | Journal of organic chemistry 2005-09, Vol.70 (19), p.7624-7628 |
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| container_end_page | 7628 |
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| container_title | Journal of organic chemistry |
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| creator | Moriarty, Robert M Albinescu, Dragos |
| description | 1α-Hydroxyvitamin D5 (1) is a promising chemopreventive agent for breast cancer and is being developed as a drug. We report a synthesis for this vitamin D analogue which uses a photochemical method for the B-ring opening, leading to the conjugated triene system. The precursor 7-dehydrositosteryl acetate (4) obtained through a one-pot, five-step procedure, was completely free of the 4,6-diene isomer that usually forms in the 5,7-diene synthesis. The pre-vitamin isomer (11) was generated using a modified two-wavelength photolysis procedure that increases the yield for this step more than 3-fold compared to classically used photolysis. The 1α-hydroxylation step was performed on the 3-triethylsilyl-trans-vitamin D5 (17) obtained via the sulfur dioxide adduct of cis-vitamin D5, in an overall yield of 48%. Photoisomerization and deprotection completed the synthesis. |
| doi_str_mv | 10.1021/jo050853f |
| format | Article |
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We report a synthesis for this vitamin D analogue which uses a photochemical method for the B-ring opening, leading to the conjugated triene system. The precursor 7-dehydrositosteryl acetate (4) obtained through a one-pot, five-step procedure, was completely free of the 4,6-diene isomer that usually forms in the 5,7-diene synthesis. The pre-vitamin isomer (11) was generated using a modified two-wavelength photolysis procedure that increases the yield for this step more than 3-fold compared to classically used photolysis. The 1α-hydroxylation step was performed on the 3-triethylsilyl-trans-vitamin D5 (17) obtained via the sulfur dioxide adduct of cis-vitamin D5, in an overall yield of 48%. Photoisomerization and deprotection completed the synthesis.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo050853f</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids ; Chemistry ; Exact sciences and technology ; General and physical chemistry ; Organic chemistry ; Photochemistry ; Physical chemistry of induced reactions (with radiations, particles and ultrasonics) ; Preparations and properties ; Steroids</subject><ispartof>Journal of organic chemistry, 2005-09, Vol.70 (19), p.7624-7628</ispartof><rights>Copyright © 2005 American Chemical Society</rights><rights>2006 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo050853f$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo050853f$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=17119098$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Moriarty, Robert M</creatorcontrib><creatorcontrib>Albinescu, Dragos</creatorcontrib><title>Synthesis of 1α-Hydroxyvitamin D5 Using a Modified Two Wavelength Photolysis for Vitamin D Formation</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>1α-Hydroxyvitamin D5 (1) is a promising chemopreventive agent for breast cancer and is being developed as a drug. We report a synthesis for this vitamin D analogue which uses a photochemical method for the B-ring opening, leading to the conjugated triene system. The precursor 7-dehydrositosteryl acetate (4) obtained through a one-pot, five-step procedure, was completely free of the 4,6-diene isomer that usually forms in the 5,7-diene synthesis. The pre-vitamin isomer (11) was generated using a modified two-wavelength photolysis procedure that increases the yield for this step more than 3-fold compared to classically used photolysis. The 1α-hydroxylation step was performed on the 3-triethylsilyl-trans-vitamin D5 (17) obtained via the sulfur dioxide adduct of cis-vitamin D5, in an overall yield of 48%. Photoisomerization and deprotection completed the synthesis.</description><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Organic chemistry</subject><subject>Photochemistry</subject><subject>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</subject><subject>Preparations and properties</subject><subject>Steroids</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNpFkMtOwkAYhSdGExFd-AazcVmdS-fSpcELJogkFHQ3GdoZGCwd0qlIH8sX8ZksQfFs_sU550v-A8AlRtcYEXyz9Ighyag9Ah3MCIp4guJj0EGIkIgSTk_BWQhL1Iox1gFm3JT1wgQXoLcQf39F_Sav_LbZuFqvXAnvGJwEV86hhs8-d9aZHKafHr7qjSlMOa8XcLTwtS-aHcP6Ck7_mvDBVytdO1-egxOri2Aufm8XTB7u014_Grw8PvVuB5HGXNYRTkSSUBGLOBM0mWlLcpIbyWLEbCzNTBJGjCEzyrDOteSax5xKgdtKC0CUdsHVnrvWIdOFrXSZuaDWlVvpqlFYYJygRLa5aJ9zoTbbg6-rd8UFFUylo7GapmTYH_I3Nfzn6iyopf-oyvYLhZHaba4Om9MfAtJy2Q</recordid><startdate>20050916</startdate><enddate>20050916</enddate><creator>Moriarty, Robert M</creator><creator>Albinescu, Dragos</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope></search><sort><creationdate>20050916</creationdate><title>Synthesis of 1α-Hydroxyvitamin D5 Using a Modified Two Wavelength Photolysis for Vitamin D Formation</title><author>Moriarty, Robert M ; Albinescu, Dragos</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a168t-1979937474c739baf2d2de85405f48eb8252ee2b351ada86a6463871374a16033</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Organic chemistry</topic><topic>Photochemistry</topic><topic>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</topic><topic>Preparations and properties</topic><topic>Steroids</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Moriarty, Robert M</creatorcontrib><creatorcontrib>Albinescu, Dragos</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Moriarty, Robert M</au><au>Albinescu, Dragos</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of 1α-Hydroxyvitamin D5 Using a Modified Two Wavelength Photolysis for Vitamin D Formation</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2005-09-16</date><risdate>2005</risdate><volume>70</volume><issue>19</issue><spage>7624</spage><epage>7628</epage><pages>7624-7628</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>1α-Hydroxyvitamin D5 (1) is a promising chemopreventive agent for breast cancer and is being developed as a drug. We report a synthesis for this vitamin D analogue which uses a photochemical method for the B-ring opening, leading to the conjugated triene system. The precursor 7-dehydrositosteryl acetate (4) obtained through a one-pot, five-step procedure, was completely free of the 4,6-diene isomer that usually forms in the 5,7-diene synthesis. The pre-vitamin isomer (11) was generated using a modified two-wavelength photolysis procedure that increases the yield for this step more than 3-fold compared to classically used photolysis. The 1α-hydroxylation step was performed on the 3-triethylsilyl-trans-vitamin D5 (17) obtained via the sulfur dioxide adduct of cis-vitamin D5, in an overall yield of 48%. Photoisomerization and deprotection completed the synthesis.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/jo050853f</doi><tpages>5</tpages></addata></record> |
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| source | American Chemical Society Journals |
| subjects | Alicyclic compounds, terpenoids, prostaglandins, steroids Chemistry Exact sciences and technology General and physical chemistry Organic chemistry Photochemistry Physical chemistry of induced reactions (with radiations, particles and ultrasonics) Preparations and properties Steroids |
| title | Synthesis of 1α-Hydroxyvitamin D5 Using a Modified Two Wavelength Photolysis for Vitamin D Formation |
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