Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks
Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to α-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic an...
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| Veröffentlicht in: | Journal of organic chemistry 2004-10, Vol.69 (22), p.7442-7447 |
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| container_title | Journal of organic chemistry |
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| creator | Paquette, Leo A Seekamp, Christopher K Kahane, Alexandra L Hilmey, David G Gallucci, Judith |
| description | Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to α-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5‘ substituent shields the β-face of the oxonium ion involved in the coupling reaction while the C3‘ substituent is projected away from the α-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable α/β spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium. |
| doi_str_mv | 10.1021/jo048904g |
| format | Article |
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These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5‘ substituent shields the β-face of the oxonium ion involved in the coupling reaction while the C3‘ substituent is projected away from the α-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable α/β spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo048904g</identifier><identifier>PMID: 15497968</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>4-Butyrolactone - analogs & derivatives ; 4-Butyrolactone - chemistry ; Carbohydrates. Nucleosides and nucleotides ; Catalysis ; Chemistry ; Crystallography, X-Ray ; DNA - chemistry ; Exact sciences and technology ; Glycosides - chemistry ; Models, Molecular ; Molecular Conformation ; Molecular Mimicry ; Molecular Structure ; Nucleosides, nucleotides and oligonucleotides ; Organic chemistry ; Preparations and properties ; Spiro Compounds - chemistry ; Stereoisomerism ; Tin Compounds - chemistry</subject><ispartof>Journal of organic chemistry, 2004-10, Vol.69 (22), p.7442-7447</ispartof><rights>Copyright © 2004 American Chemical Society</rights><rights>2005 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a379t-53c2d65d785def35f55f4b903bf51b461e0cb39712a64f498507887b1ca1555c3</citedby><cites>FETCH-LOGICAL-a379t-53c2d65d785def35f55f4b903bf51b461e0cb39712a64f498507887b1ca1555c3</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/jo048904g$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo048904g$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=16219197$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15497968$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Paquette, Leo A</creatorcontrib><creatorcontrib>Seekamp, Christopher K</creatorcontrib><creatorcontrib>Kahane, Alexandra L</creatorcontrib><creatorcontrib>Hilmey, David G</creatorcontrib><creatorcontrib>Gallucci, Judith</creatorcontrib><title>Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to α-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5‘ substituent shields the β-face of the oxonium ion involved in the coupling reaction while the C3‘ substituent is projected away from the α-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable α/β spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium.</description><subject>4-Butyrolactone - analogs & derivatives</subject><subject>4-Butyrolactone - chemistry</subject><subject>Carbohydrates. Nucleosides and nucleotides</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Crystallography, X-Ray</subject><subject>DNA - chemistry</subject><subject>Exact sciences and technology</subject><subject>Glycosides - chemistry</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Molecular Mimicry</subject><subject>Molecular Structure</subject><subject>Nucleosides, nucleotides and oligonucleotides</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Spiro Compounds - chemistry</subject><subject>Stereoisomerism</subject><subject>Tin Compounds - chemistry</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0MFu0zAYB3ALgVgZHHgBlAtIHAJ2HNvxsRt0nVTBpBbEzXIce3hz4uIvGezGY_B8PAmuWq0XfLEs__TX9_0ReknwO4Ir8v4m4rqRuL5-hGaEVbjk-fEYzTCuqpJWnJ6gZwA3OB_G2FN0QlgtheTNDMX1aJON5rvtvdGhWFg9TslCEV2xsj89FHPju_IqxT6Otisuwr2J4Ds9-jhAcTncxXDnh-ui_vv7T7ne-hT1MExB7_CHT_PibPKh24GzEM0tPEdPnA5gXxzuU_Rl8XFzvixXny8uz-erUlMhx5JRU3WcdaJhnXWUOcZc3UpMW8dIW3NisWmpFKTSvHa1bBgWTSNaYjTJKxp6it7sc7cp_pgsjKr3YGwIerBxAsW5zA1ImuHbPTQpAiTr1Db5Xqd7RbDatase2s321SF0anvbHeWhzgxeH4CG3KZLejAejo5XRBIpsiv3zsNofz3863SruKCCqc3VWtHNt-XXZrFU5JirDeR5pjTk7v4z4D8IhZ4u</recordid><startdate>20041029</startdate><enddate>20041029</enddate><creator>Paquette, Leo A</creator><creator>Seekamp, Christopher K</creator><creator>Kahane, Alexandra L</creator><creator>Hilmey, David G</creator><creator>Gallucci, Judith</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20041029</creationdate><title>Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks</title><author>Paquette, Leo A ; Seekamp, Christopher K ; Kahane, Alexandra L ; Hilmey, David G ; Gallucci, Judith</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-53c2d65d785def35f55f4b903bf51b461e0cb39712a64f498507887b1ca1555c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2004</creationdate><topic>4-Butyrolactone - analogs & derivatives</topic><topic>4-Butyrolactone - chemistry</topic><topic>Carbohydrates. Nucleosides and nucleotides</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Crystallography, X-Ray</topic><topic>DNA - chemistry</topic><topic>Exact sciences and technology</topic><topic>Glycosides - chemistry</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Molecular Mimicry</topic><topic>Molecular Structure</topic><topic>Nucleosides, nucleotides and oligonucleotides</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Spiro Compounds - chemistry</topic><topic>Stereoisomerism</topic><topic>Tin Compounds - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Paquette, Leo A</creatorcontrib><creatorcontrib>Seekamp, Christopher K</creatorcontrib><creatorcontrib>Kahane, Alexandra L</creatorcontrib><creatorcontrib>Hilmey, David G</creatorcontrib><creatorcontrib>Gallucci, Judith</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Paquette, Leo A</au><au>Seekamp, Christopher K</au><au>Kahane, Alexandra L</au><au>Hilmey, David G</au><au>Gallucci, Judith</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2004-10-29</date><risdate>2004</risdate><volume>69</volume><issue>22</issue><spage>7442</spage><epage>7447</epage><pages>7442-7447</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to α-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5‘ substituent shields the β-face of the oxonium ion involved in the coupling reaction while the C3‘ substituent is projected away from the α-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable α/β spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>15497968</pmid><doi>10.1021/jo048904g</doi><tpages>6</tpages></addata></record> |
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| subjects | 4-Butyrolactone - analogs & derivatives 4-Butyrolactone - chemistry Carbohydrates. Nucleosides and nucleotides Catalysis Chemistry Crystallography, X-Ray DNA - chemistry Exact sciences and technology Glycosides - chemistry Models, Molecular Molecular Conformation Molecular Mimicry Molecular Structure Nucleosides, nucleotides and oligonucleotides Organic chemistry Preparations and properties Spiro Compounds - chemistry Stereoisomerism Tin Compounds - chemistry |
| title | Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks |
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