Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides

Reactions of organosilicon reagents (such as allyltrimethylsilane, silyl enol ethers, cyanotrimethylsilane) with 3‘,4‘-unsaturated nucleosides (of uracil, N 4-acetylcytosine, and hypoxanthine) having an allyl ester structure were investigated in the presence of a Lewis acid in CH2Cl2. In the cases o...

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Veröffentlicht in:Journal of organic chemistry 1996-02, Vol.61 (3), p.851-858
Hauptverfasser: Haraguchi, Kazuhiro, Tanaka, Hiromichi, Itoh, Yoshiharu, Yamaguchi, Kentaro, Miyasaka, Tadashi
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container_end_page 858
container_issue 3
container_start_page 851
container_title Journal of organic chemistry
container_volume 61
creator Haraguchi, Kazuhiro
Tanaka, Hiromichi
Itoh, Yoshiharu
Yamaguchi, Kentaro
Miyasaka, Tadashi
description Reactions of organosilicon reagents (such as allyltrimethylsilane, silyl enol ethers, cyanotrimethylsilane) with 3‘,4‘-unsaturated nucleosides (of uracil, N 4-acetylcytosine, and hypoxanthine) having an allyl ester structure were investigated in the presence of a Lewis acid in CH2Cl2. In the cases of uracil and N 4-acetylcytosine derivatives, SnCl4 appeared to be suitable, whereas the use of EtAlCl2 was necessary for the hypoxanthine derivatives. The main pathway of these reactions was found to be α-face-selective SN2‘ allylic substitution, irrespective of the configuration of 2‘-O-acyl leaving group. As a result, a new stereoselective operation for C−C bonds formation leading to 4‘-carbon-substituted 2‘,3‘-didehydro-2‘,3‘-dideoxyribonucleosides has been disclosed for the first time. Stereochemistry of these 4‘-C-branched products can be assigned on the basis of 1H NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5‘-O-(tert-butyldiphenylsilyl) protecting group.
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In the cases of uracil and N 4-acetylcytosine derivatives, SnCl4 appeared to be suitable, whereas the use of EtAlCl2 was necessary for the hypoxanthine derivatives. The main pathway of these reactions was found to be α-face-selective SN2‘ allylic substitution, irrespective of the configuration of 2‘-O-acyl leaving group. As a result, a new stereoselective operation for C−C bonds formation leading to 4‘-carbon-substituted 2‘,3‘-didehydro-2‘,3‘-dideoxyribonucleosides has been disclosed for the first time. Stereochemistry of these 4‘-C-branched products can be assigned on the basis of 1H NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5‘-O-(tert-butyldiphenylsilyl) protecting group.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo9516190</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Journal of organic chemistry, 1996-02, Vol.61 (3), p.851-858</ispartof><rights>Copyright © 1996 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a276t-7d3e141c8cba76719936b47e30cd8bce4974f24f6a167afea7280bfa725ca9943</citedby><cites>FETCH-LOGICAL-a276t-7d3e141c8cba76719936b47e30cd8bce4974f24f6a167afea7280bfa725ca9943</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/jo9516190$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo9516190$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids></links><search><creatorcontrib>Haraguchi, Kazuhiro</creatorcontrib><creatorcontrib>Tanaka, Hiromichi</creatorcontrib><creatorcontrib>Itoh, Yoshiharu</creatorcontrib><creatorcontrib>Yamaguchi, Kentaro</creatorcontrib><creatorcontrib>Miyasaka, Tadashi</creatorcontrib><title>Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides</title><title>Journal of organic chemistry</title><addtitle>J. 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Stereochemistry of these 4‘-C-branched products can be assigned on the basis of 1H NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5‘-O-(tert-butyldiphenylsilyl) protecting group.</description><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1996</creationdate><recordtype>article</recordtype><recordid>eNptkL9OwzAQhy0EEqUw8AZZGJAw2E5ix2xt-StVFNR2YYkcx6EpIUa2g9qtK2_AY_BMfRJcitqFG-7k06fvJx8AxxidY0TwxVTzGFPM0Q5o4ZggSDmKdkELIUJgSGi4Dw6snSJfcRy3wHenquZVKYNhk1lXusaVug50EYTLxddZ5Bsc11a4xgin8uChkZXStsyVvVwuPoOBeRG1f3uDrmFXWM8MnTKeUZWSrvxQQUdKZW3gdPCr68GuEbWceJKsMlZB8MobJ_PcaLjd5X6nZ3NTZrrexh6CvUJUVh39zTYY31yPenewP7i973X6UBBGHWR5qHCEZSIzwSjDnIc0i5gKkcyTTKqIs6ggUUEFpkwUSjCSoKzwI5aC8yhsg9O1VxptrVFF-m7KN2HmKUbp6tTp5tSehWu2tE7NNqAwryllIYvT0eMwfR4l5Ikmj2nX8ydrXkjrNY2p_U_-8f4ALxuV2A</recordid><startdate>19960209</startdate><enddate>19960209</enddate><creator>Haraguchi, Kazuhiro</creator><creator>Tanaka, Hiromichi</creator><creator>Itoh, Yoshiharu</creator><creator>Yamaguchi, Kentaro</creator><creator>Miyasaka, Tadashi</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19960209</creationdate><title>Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides</title><author>Haraguchi, Kazuhiro ; Tanaka, Hiromichi ; Itoh, Yoshiharu ; Yamaguchi, Kentaro ; Miyasaka, Tadashi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a276t-7d3e141c8cba76719936b47e30cd8bce4974f24f6a167afea7280bfa725ca9943</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1996</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Haraguchi, Kazuhiro</creatorcontrib><creatorcontrib>Tanaka, Hiromichi</creatorcontrib><creatorcontrib>Itoh, Yoshiharu</creatorcontrib><creatorcontrib>Yamaguchi, Kentaro</creatorcontrib><creatorcontrib>Miyasaka, Tadashi</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Haraguchi, Kazuhiro</au><au>Tanaka, Hiromichi</au><au>Itoh, Yoshiharu</au><au>Yamaguchi, Kentaro</au><au>Miyasaka, Tadashi</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>1996-02-09</date><risdate>1996</risdate><volume>61</volume><issue>3</issue><spage>851</spage><epage>858</epage><pages>851-858</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>Reactions of organosilicon reagents (such as allyltrimethylsilane, silyl enol ethers, cyanotrimethylsilane) with 3‘,4‘-unsaturated nucleosides (of uracil, N 4-acetylcytosine, and hypoxanthine) having an allyl ester structure were investigated in the presence of a Lewis acid in CH2Cl2. In the cases of uracil and N 4-acetylcytosine derivatives, SnCl4 appeared to be suitable, whereas the use of EtAlCl2 was necessary for the hypoxanthine derivatives. The main pathway of these reactions was found to be α-face-selective SN2‘ allylic substitution, irrespective of the configuration of 2‘-O-acyl leaving group. As a result, a new stereoselective operation for C−C bonds formation leading to 4‘-carbon-substituted 2‘,3‘-didehydro-2‘,3‘-dideoxyribonucleosides has been disclosed for the first time. Stereochemistry of these 4‘-C-branched products can be assigned on the basis of 1H NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5‘-O-(tert-butyldiphenylsilyl) protecting group.</abstract><pub>American Chemical Society</pub><doi>10.1021/jo9516190</doi><tpages>8</tpages></addata></record>
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title Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides
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