The Stereochemical Outcome of Electrophilic Addition Reactions on the 5,6-Double Bond in the Spinosyns
The electrophilic addition of reagents to the 5,6-double bond in spinosyn A and spinosyn D systems occurred with high π-diastereofacial selectivity. Addition occurred preferentially from the β face of the molecule with selectivities ranging from 5:1 to better than 30:1. Various NMR properties were i...
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| Veröffentlicht in: | Journal of organic chemistry 2001-12, Vol.66 (25), p.8431-8435 |
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| container_end_page | 8435 |
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| container_issue | 25 |
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| container_title | Journal of organic chemistry |
| container_volume | 66 |
| creator | De Amicis, Carl V Graupner, Paul R Erickson, Jon A Paschal, Jonathon W Kirst, Herbert A Creemer, Lawrence C Fanwick, Phillip E |
| description | The electrophilic addition of reagents to the 5,6-double bond in spinosyn A and spinosyn D systems occurred with high π-diastereofacial selectivity. Addition occurred preferentially from the β face of the molecule with selectivities ranging from 5:1 to better than 30:1. Various NMR properties were investigated in order to distinguish the β and α isomers with the help of theoretical models of the products. These NMR properties include a 13C γ effect to C-11 and vicinal coupling between H-4 and H-5. To help rationalize the selectivity, computational studies on the transition states for epoxidation were calculated using density functional theory. The results indicate that β epoxidation is favored and that the geometries of the transition structures are consistent with torsional steering being the source of the selectivity. |
| doi_str_mv | 10.1021/jo015830p |
| format | Article |
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Addition occurred preferentially from the β face of the molecule with selectivities ranging from 5:1 to better than 30:1. Various NMR properties were investigated in order to distinguish the β and α isomers with the help of theoretical models of the products. These NMR properties include a 13C γ effect to C-11 and vicinal coupling between H-4 and H-5. To help rationalize the selectivity, computational studies on the transition states for epoxidation were calculated using density functional theory. The results indicate that β epoxidation is favored and that the geometries of the transition structures are consistent with torsional steering being the source of the selectivity.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo015830p</identifier><identifier>PMID: 11735521</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Anti-Bacterial Agents - chemical synthesis ; Crystallography, X-Ray ; Electrochemistry ; Epoxy Compounds - chemistry ; Indicators and Reagents ; Macrolides ; Magnetic Resonance Spectroscopy ; Molecular Conformation ; Saccharopolyspora - chemistry</subject><ispartof>Journal of organic chemistry, 2001-12, Vol.66 (25), p.8431-8435</ispartof><rights>Copyright © 2001 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a349t-4ca3661c2fda32ee1fa868147f76c35acde67e0b318faa59d1a0f93d71b1c1563</citedby><cites>FETCH-LOGICAL-a349t-4ca3661c2fda32ee1fa868147f76c35acde67e0b318faa59d1a0f93d71b1c1563</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/jo015830p$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo015830p$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11735521$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>De Amicis, Carl V</creatorcontrib><creatorcontrib>Graupner, Paul R</creatorcontrib><creatorcontrib>Erickson, Jon A</creatorcontrib><creatorcontrib>Paschal, Jonathon W</creatorcontrib><creatorcontrib>Kirst, Herbert A</creatorcontrib><creatorcontrib>Creemer, Lawrence C</creatorcontrib><creatorcontrib>Fanwick, Phillip E</creatorcontrib><title>The Stereochemical Outcome of Electrophilic Addition Reactions on the 5,6-Double Bond in the Spinosyns</title><title>Journal of organic chemistry</title><addtitle>J. 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The results indicate that β epoxidation is favored and that the geometries of the transition structures are consistent with torsional steering being the source of the selectivity.</description><subject>Anti-Bacterial Agents - chemical synthesis</subject><subject>Crystallography, X-Ray</subject><subject>Electrochemistry</subject><subject>Epoxy Compounds - chemistry</subject><subject>Indicators and Reagents</subject><subject>Macrolides</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Molecular Conformation</subject><subject>Saccharopolyspora - chemistry</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkM1u1DAUhS0EotOWBS-AvAEJiYCvHTvJsi2lRa0oYgYJsbE8zrXGJYmDnUjt29dVRmXD3dy_T-dIh5DXwD4C4_DpNjCQtWDjM7ICyVmhGlY-JyvGOC8EV-KAHKZ0y3JJKV-SA4BKSMlhRdxmh3Q9YcRgd9h7azp6M0829EiDo-cd2imGcec7b-lJ2_rJh4H-QGMfh0TzMmUF-UEVn8O87ZCehqGlfjmvRz-EdD-kY_LCmS7hq30_Ij-_nG_OLovrm4uvZyfXhRFlMxWlNUIpsNy1RnBEcKZWNZSVq5QV0tgWVYVsK6B2xsimBcNcI9oKtmBBKnFE3i26Ywx_Z0yT7n2y2HVmwDAnXXFRcq5kBt8voI0hpYhOj9H3Jt5rYPoxVP0Uambf7EXnbY_tP3KfYgaKBfBpwrunv4l_tKpEJfXm-1pf1ep38-sb01eZf7vwxqbsM8chZ_If4wd2eI0Q</recordid><startdate>20011214</startdate><enddate>20011214</enddate><creator>De Amicis, Carl V</creator><creator>Graupner, Paul R</creator><creator>Erickson, Jon A</creator><creator>Paschal, Jonathon W</creator><creator>Kirst, Herbert A</creator><creator>Creemer, Lawrence C</creator><creator>Fanwick, Phillip E</creator><general>American Chemical Society</general><scope>BSCLL</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>20011214</creationdate><title>The Stereochemical Outcome of Electrophilic Addition Reactions on the 5,6-Double Bond in the Spinosyns</title><author>De Amicis, Carl V ; Graupner, Paul R ; Erickson, Jon A ; Paschal, Jonathon W ; Kirst, Herbert A ; Creemer, Lawrence C ; Fanwick, Phillip E</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a349t-4ca3661c2fda32ee1fa868147f76c35acde67e0b318faa59d1a0f93d71b1c1563</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Anti-Bacterial Agents - chemical synthesis</topic><topic>Crystallography, X-Ray</topic><topic>Electrochemistry</topic><topic>Epoxy Compounds - chemistry</topic><topic>Indicators and Reagents</topic><topic>Macrolides</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Molecular Conformation</topic><topic>Saccharopolyspora - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>De Amicis, Carl V</creatorcontrib><creatorcontrib>Graupner, Paul R</creatorcontrib><creatorcontrib>Erickson, Jon A</creatorcontrib><creatorcontrib>Paschal, Jonathon W</creatorcontrib><creatorcontrib>Kirst, Herbert A</creatorcontrib><creatorcontrib>Creemer, Lawrence C</creatorcontrib><creatorcontrib>Fanwick, Phillip E</creatorcontrib><collection>Istex</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>De Amicis, Carl V</au><au>Graupner, Paul R</au><au>Erickson, Jon A</au><au>Paschal, Jonathon W</au><au>Kirst, Herbert A</au><au>Creemer, Lawrence C</au><au>Fanwick, Phillip E</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The Stereochemical Outcome of Electrophilic Addition Reactions on the 5,6-Double Bond in the Spinosyns</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2001-12-14</date><risdate>2001</risdate><volume>66</volume><issue>25</issue><spage>8431</spage><epage>8435</epage><pages>8431-8435</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>The electrophilic addition of reagents to the 5,6-double bond in spinosyn A and spinosyn D systems occurred with high π-diastereofacial selectivity. Addition occurred preferentially from the β face of the molecule with selectivities ranging from 5:1 to better than 30:1. Various NMR properties were investigated in order to distinguish the β and α isomers with the help of theoretical models of the products. These NMR properties include a 13C γ effect to C-11 and vicinal coupling between H-4 and H-5. To help rationalize the selectivity, computational studies on the transition states for epoxidation were calculated using density functional theory. The results indicate that β epoxidation is favored and that the geometries of the transition structures are consistent with torsional steering being the source of the selectivity.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>11735521</pmid><doi>10.1021/jo015830p</doi><tpages>5</tpages></addata></record> |
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| language | eng |
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| source | ACS Publications; MEDLINE |
| subjects | Anti-Bacterial Agents - chemical synthesis Crystallography, X-Ray Electrochemistry Epoxy Compounds - chemistry Indicators and Reagents Macrolides Magnetic Resonance Spectroscopy Molecular Conformation Saccharopolyspora - chemistry |
| title | The Stereochemical Outcome of Electrophilic Addition Reactions on the 5,6-Double Bond in the Spinosyns |
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