Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers
The method of continuous variation was used to characterize lithium enolates, phenolates, carboxylates, and alkoxides solvated by N,N,N′,N′-tetramethylethylenediamine (TMEDA). The method relies on characterizing an ensemble of homo- and heteroaggregates using 6Li NMR spectroscopy. A combination of a...
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| Veröffentlicht in: | Journal of organic chemistry 2008-10, Vol.73 (19), p.7743-7747 |
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| container_title | Journal of organic chemistry |
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| creator | Gruver, Jocelyn M Liou, Lara R McNeil, Anne J Ramirez, Antonio Collum, David B |
| description | The method of continuous variation was used to characterize lithium enolates, phenolates, carboxylates, and alkoxides solvated by N,N,N′,N′-tetramethylethylenediamine (TMEDA). The method relies on characterizing an ensemble of homo- and heteroaggregates using 6Li NMR spectroscopy. A combination of aggregate counts and symmetries, nearly statistical distributions, and quantitative parametric fits revealed that cyclic dimers are the dominant forms. Nonstatistical distributions favoring heteroaggregated dimers were observed when hindered enolates and carboxylates were mixed with unhindered enolates. Hindered (tertiary) alkoxides form higher aggregates (possibly hexamers), whereas hindered lithium phenolates appear to form TMEDA-solvated monomers. |
| doi_str_mv | 10.1021/jo801532d |
| format | Article |
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The method relies on characterizing an ensemble of homo- and heteroaggregates using 6Li NMR spectroscopy. A combination of aggregate counts and symmetries, nearly statistical distributions, and quantitative parametric fits revealed that cyclic dimers are the dominant forms. Nonstatistical distributions favoring heteroaggregated dimers were observed when hindered enolates and carboxylates were mixed with unhindered enolates. 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Org. Chem</addtitle><description>The method of continuous variation was used to characterize lithium enolates, phenolates, carboxylates, and alkoxides solvated by N,N,N′,N′-tetramethylethylenediamine (TMEDA). The method relies on characterizing an ensemble of homo- and heteroaggregates using 6Li NMR spectroscopy. A combination of aggregate counts and symmetries, nearly statistical distributions, and quantitative parametric fits revealed that cyclic dimers are the dominant forms. Nonstatistical distributions favoring heteroaggregated dimers were observed when hindered enolates and carboxylates were mixed with unhindered enolates. Hindered (tertiary) alkoxides form higher aggregates (possibly hexamers), whereas hindered lithium phenolates appear to form TMEDA-solvated monomers.</description><subject>Carboxylic Acids - chemistry</subject><subject>Chemistry</subject><subject>Dimerization</subject><subject>Ethylenediamines - chemistry</subject><subject>Exact sciences and technology</subject><subject>Hydroxybenzoates - chemistry</subject><subject>Lithium</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Molecular Structure</subject><subject>Noncondensed benzenic compounds</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Solutions - chemistry</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkc2O0zAQxyMEYsvCgRdAvoCEtAE7iZ2EA1LV_QBRQaUWiZvlOhPqXcdebGfV3vZ9uPFIPAkuDVmQ8EhjW_Obv8czSfKU4FcEZ-T1pa0woXnW3EsmhGY4ZTUu7icTjLMszTOWHyWPvL_EcVFKHyZHpCorUpFsknxfWt0HZQ1aBtfL0DvwyLZorsJG9R06M1aLAP4ELTYwnmfCre12N9yEadBUX9mtamKyMihsAC2iEBgJe7GPJ9F-3v747dIVBCc6CJudPjgDjRKdMvAGTfd5N0L_yZztpFYSnaoOnH-cPGiF9vBk2I-Tz-dnq9m7dP7p4v1sOk8FzcuQrkmZ07osRJaVbY0pYYQyJmizBlFKCWVsEdSibuu6IXXREMkgGivyoqBN2-bHyduD7nW_7qCRYGLBml871Qm341Yo_m_EqA3_am947DSriioKvBgEnP3Wgw-8U16C1sKA7T1nNcNFSfbgywMonfXeQTs-QjDfj5aPo43ss7-ruiOHWUbg-QAIL4VunTBS-ZHLcPw4xXXk0gOnfIDtGBfuirMyLylfLZYcr76cX3woKp7f6QrpYz29M7H5_ynwFxgwy9M</recordid><startdate>20081003</startdate><enddate>20081003</enddate><creator>Gruver, Jocelyn M</creator><creator>Liou, Lara R</creator><creator>McNeil, Anne J</creator><creator>Ramirez, Antonio</creator><creator>Collum, David B</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><scope>5PM</scope></search><sort><creationdate>20081003</creationdate><title>Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers</title><author>Gruver, Jocelyn M ; Liou, Lara R ; McNeil, Anne J ; Ramirez, Antonio ; Collum, David B</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a537t-b1735974a227f905161566a5dbea7cce7152e9a9f99d194d1c6e6e6643445dff3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Carboxylic Acids - chemistry</topic><topic>Chemistry</topic><topic>Dimerization</topic><topic>Ethylenediamines - chemistry</topic><topic>Exact sciences and technology</topic><topic>Hydroxybenzoates - chemistry</topic><topic>Lithium</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Molecular Structure</topic><topic>Noncondensed benzenic compounds</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Solutions - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gruver, Jocelyn M</creatorcontrib><creatorcontrib>Liou, Lara R</creatorcontrib><creatorcontrib>McNeil, Anne J</creatorcontrib><creatorcontrib>Ramirez, Antonio</creatorcontrib><creatorcontrib>Collum, David B</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><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gruver, Jocelyn M</au><au>Liou, Lara R</au><au>McNeil, Anne J</au><au>Ramirez, Antonio</au><au>Collum, David B</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2008-10-03</date><risdate>2008</risdate><volume>73</volume><issue>19</issue><spage>7743</spage><epage>7747</epage><pages>7743-7747</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>The method of continuous variation was used to characterize lithium enolates, phenolates, carboxylates, and alkoxides solvated by N,N,N′,N′-tetramethylethylenediamine (TMEDA). The method relies on characterizing an ensemble of homo- and heteroaggregates using 6Li NMR spectroscopy. A combination of aggregate counts and symmetries, nearly statistical distributions, and quantitative parametric fits revealed that cyclic dimers are the dominant forms. Nonstatistical distributions favoring heteroaggregated dimers were observed when hindered enolates and carboxylates were mixed with unhindered enolates. 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| source | ACS Publications; MEDLINE |
| subjects | Carboxylic Acids - chemistry Chemistry Dimerization Ethylenediamines - chemistry Exact sciences and technology Hydroxybenzoates - chemistry Lithium Magnetic Resonance Spectroscopy Molecular Structure Noncondensed benzenic compounds Organic chemistry Preparations and properties Solutions - chemistry |
| title | Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers |
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