CeCl3/n‐BuLi: Unraveling Imamoto's Organocerium Reagent
CeCl3(thf) reacts at low temperatures with MeLi, t‐BuLi, and n‐BuLi to isolable organocerium complexes. Solvent‐dependent extensive n‐BuLi dissociation is revealed by 7Li NMR spectroscopy, suggesting “Ce(n‐Bu)3(thf)x” or solvent‐separated ion pairs like “[Li(thf)4][Ce(n‐Bu)4(thf)y]” as the dominant...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2021-07, Vol.60 (28), p.15622-15631 |
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| creator | Berger, Tassilo Lebon, Jakob Maichle‐Mössmer, Cäcilia Anwander, Reiner |
| description | CeCl3(thf) reacts at low temperatures with MeLi, t‐BuLi, and n‐BuLi to isolable organocerium complexes. Solvent‐dependent extensive n‐BuLi dissociation is revealed by 7Li NMR spectroscopy, suggesting “Ce(n‐Bu)3(thf)x” or solvent‐separated ion pairs like “[Li(thf)4][Ce(n‐Bu)4(thf)y]” as the dominant species of the Imamoto reagent. The stability of complexes Li3Ln(n‐Bu)6(thf)4 increases markedly with decreasing LnIII size. Closer inspection of the solution behavior of crystalline Li3Lu(n‐Bu)6(thf)4 and mixtures of LuCl3(thf)2/n‐BuLi in THF indicates occurring n‐BuLi dissociation only at molar ratios of |
| doi_str_mv | 10.1002/anie.202103889 |
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Seamless low‐temperature syntheses, crystallization and spectroscopies provide structural details of the heterobimetallic reagent routinely used for regioselective carbon−carbon bond forming reactions with carbonyl compounds. 7Li NMR spectroscopy takes on an important role here, tracking down n‐BuLi dissociation.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202103889</identifier><identifier>PMID: 33905590</identifier><language>eng</language><publisher>WEINHEIM: Wiley</publisher><subject>7Li NMR spectroscopy ; carbonyl alkylation ; cerium ; Chemistry ; Chemistry, Multidisciplinary ; Dominant species ; Inspection ; Ion pairs ; lithium ; Lithium chloride ; Low temperature ; Magnetic resonance spectroscopy ; n-butyl ; NMR ; NMR spectroscopy ; Nuclear magnetic resonance ; Physical Sciences ; Reagents ; Science & Technology ; Solvents</subject><ispartof>Angewandte Chemie International Edition, 2021-07, Vol.60 (28), p.15622-15631</ispartof><rights>2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH</rights><rights>2021 Wiley-VCH GmbH.</rights><rights>2021. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>true</woscitedreferencessubscribed><woscitedreferencescount>18</woscitedreferencescount><woscitedreferencesoriginalsourcerecordid>wos000658787700001</woscitedreferencesoriginalsourcerecordid><cites>FETCH-LOGICAL-p3849-eb2cab40ad198fda399104dcd25fe70cdc952a594dee679a0e35bbd315aa98543</cites><orcidid>0000-0002-1543-3787 ; 0000-0001-5830-7177 ; 0000-0003-1092-5528 ; 0000-0001-7638-1610</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202103889$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202103889$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,777,781,882,1412,27905,27906,45555,45556</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33905590$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Berger, Tassilo</creatorcontrib><creatorcontrib>Lebon, Jakob</creatorcontrib><creatorcontrib>Maichle‐Mössmer, Cäcilia</creatorcontrib><creatorcontrib>Anwander, Reiner</creatorcontrib><title>CeCl3/n‐BuLi: Unraveling Imamoto's Organocerium Reagent</title><title>Angewandte Chemie International Edition</title><addtitle>ANGEW CHEM INT EDIT</addtitle><addtitle>Angew Chem Int Ed Engl</addtitle><description>CeCl3(thf) reacts at low temperatures with MeLi, t‐BuLi, and n‐BuLi to isolable organocerium complexes. Solvent‐dependent extensive n‐BuLi dissociation is revealed by 7Li NMR spectroscopy, suggesting “Ce(n‐Bu)3(thf)x” or solvent‐separated ion pairs like “[Li(thf)4][Ce(n‐Bu)4(thf)y]” as the dominant species of the Imamoto reagent. The stability of complexes Li3Ln(n‐Bu)6(thf)4 increases markedly with decreasing LnIII size. Closer inspection of the solution behavior of crystalline Li3Lu(n‐Bu)6(thf)4 and mixtures of LuCl3(thf)2/n‐BuLi in THF indicates occurring n‐BuLi dissociation only at molar ratios of <1:3. n‐BuLi‐depleted complex LiLu(n‐Bu)3Cl(tmeda)2 was obtained by treatment of Li2Lu(n‐Bu)5(tmeda)2 with ClSiMe3, at the expense of LiCl incorporation. Imamoto's ketone/tertiary alcohol transformation was examined with 1,3‐diphenylpropan‐2‐one, affording 99 % of alcohol.
Seamless low‐temperature syntheses, crystallization and spectroscopies provide structural details of the heterobimetallic reagent routinely used for regioselective carbon−carbon bond forming reactions with carbonyl compounds. 7Li NMR spectroscopy takes on an important role here, tracking down n‐BuLi dissociation.</description><subject>7Li NMR spectroscopy</subject><subject>carbonyl alkylation</subject><subject>cerium</subject><subject>Chemistry</subject><subject>Chemistry, Multidisciplinary</subject><subject>Dominant species</subject><subject>Inspection</subject><subject>Ion pairs</subject><subject>lithium</subject><subject>Lithium chloride</subject><subject>Low temperature</subject><subject>Magnetic resonance spectroscopy</subject><subject>n-butyl</subject><subject>NMR</subject><subject>NMR spectroscopy</subject><subject>Nuclear magnetic resonance</subject><subject>Physical Sciences</subject><subject>Reagents</subject><subject>Science & Technology</subject><subject>Solvents</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><sourceid>HGBXW</sourceid><recordid>eNqNkk1rFTEUhoMo9kO3LuWCixZk2nxOEheFOlR74WJB7DqcyZx7TZlJrvNR6c6f4G_0l5jS61BducoJed73nBxeQl4xesIo5acQA55wyhkVxtgnZJ8pzgqhtXiaaylEoY1ie-RgGG4ybwwtn5M9ISxVytJ9YiusWnEaf_34-X5ahXeL69jDLbYhbhbLDro0pqNhcdVvICaPfZi6xWeEDcbxBXm2hnbAl7vzkFx_uPhSXRarq4_L6nxVbIWRtsCae6glhYZZs25AWMuobHzD1Ro19Y23ioOyskEstQWKQtV1I5gCsEZJcUjOHny3U91h43PrHlq37UMH_Z1LENzfLzF8dZt064wo81rKbHC8M-jTtwmH0XVh8Ni2EDFNg-OKWcHL0tiMvvkHvUlTH_P3MiWV1KXUIlOvH080j_Jnqxl4-wB8xzqtBx8wepwxSmmpjDZa54qyTJv_p6swwhhSrNIUxyy1O2lo8W7WMOruw-Huw-HmcLjzT8uL-SZ-A5WVq8s</recordid><startdate>20210705</startdate><enddate>20210705</enddate><creator>Berger, Tassilo</creator><creator>Lebon, Jakob</creator><creator>Maichle‐Mössmer, Cäcilia</creator><creator>Anwander, Reiner</creator><general>Wiley</general><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><scope>WIN</scope><scope>BLEPL</scope><scope>DTL</scope><scope>HGBXW</scope><scope>NPM</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-1543-3787</orcidid><orcidid>https://orcid.org/0000-0001-5830-7177</orcidid><orcidid>https://orcid.org/0000-0003-1092-5528</orcidid><orcidid>https://orcid.org/0000-0001-7638-1610</orcidid></search><sort><creationdate>20210705</creationdate><title>CeCl3/n‐BuLi: Unraveling Imamoto's Organocerium Reagent</title><author>Berger, Tassilo ; Lebon, Jakob ; Maichle‐Mössmer, Cäcilia ; Anwander, Reiner</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p3849-eb2cab40ad198fda399104dcd25fe70cdc952a594dee679a0e35bbd315aa98543</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>7Li NMR spectroscopy</topic><topic>carbonyl alkylation</topic><topic>cerium</topic><topic>Chemistry</topic><topic>Chemistry, Multidisciplinary</topic><topic>Dominant species</topic><topic>Inspection</topic><topic>Ion pairs</topic><topic>lithium</topic><topic>Lithium chloride</topic><topic>Low temperature</topic><topic>Magnetic resonance spectroscopy</topic><topic>n-butyl</topic><topic>NMR</topic><topic>NMR spectroscopy</topic><topic>Nuclear magnetic resonance</topic><topic>Physical Sciences</topic><topic>Reagents</topic><topic>Science & Technology</topic><topic>Solvents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Berger, Tassilo</creatorcontrib><creatorcontrib>Lebon, Jakob</creatorcontrib><creatorcontrib>Maichle‐Mössmer, Cäcilia</creatorcontrib><creatorcontrib>Anwander, Reiner</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>Wiley Online Library Free Content</collection><collection>Web of Science Core Collection</collection><collection>Science Citation Index Expanded</collection><collection>Web of Science - Science Citation Index Expanded - 2021</collection><collection>PubMed</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Berger, Tassilo</au><au>Lebon, Jakob</au><au>Maichle‐Mössmer, Cäcilia</au><au>Anwander, Reiner</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>CeCl3/n‐BuLi: Unraveling Imamoto's Organocerium Reagent</atitle><jtitle>Angewandte Chemie International Edition</jtitle><stitle>ANGEW CHEM INT EDIT</stitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2021-07-05</date><risdate>2021</risdate><volume>60</volume><issue>28</issue><spage>15622</spage><epage>15631</epage><pages>15622-15631</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>CeCl3(thf) reacts at low temperatures with MeLi, t‐BuLi, and n‐BuLi to isolable organocerium complexes. Solvent‐dependent extensive n‐BuLi dissociation is revealed by 7Li NMR spectroscopy, suggesting “Ce(n‐Bu)3(thf)x” or solvent‐separated ion pairs like “[Li(thf)4][Ce(n‐Bu)4(thf)y]” as the dominant species of the Imamoto reagent. The stability of complexes Li3Ln(n‐Bu)6(thf)4 increases markedly with decreasing LnIII size. Closer inspection of the solution behavior of crystalline Li3Lu(n‐Bu)6(thf)4 and mixtures of LuCl3(thf)2/n‐BuLi in THF indicates occurring n‐BuLi dissociation only at molar ratios of <1:3. n‐BuLi‐depleted complex LiLu(n‐Bu)3Cl(tmeda)2 was obtained by treatment of Li2Lu(n‐Bu)5(tmeda)2 with ClSiMe3, at the expense of LiCl incorporation. Imamoto's ketone/tertiary alcohol transformation was examined with 1,3‐diphenylpropan‐2‐one, affording 99 % of alcohol.
Seamless low‐temperature syntheses, crystallization and spectroscopies provide structural details of the heterobimetallic reagent routinely used for regioselective carbon−carbon bond forming reactions with carbonyl compounds. 7Li NMR spectroscopy takes on an important role here, tracking down n‐BuLi dissociation.</abstract><cop>WEINHEIM</cop><pub>Wiley</pub><pmid>33905590</pmid><doi>10.1002/anie.202103889</doi><tpages>10</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-1543-3787</orcidid><orcidid>https://orcid.org/0000-0001-5830-7177</orcidid><orcidid>https://orcid.org/0000-0003-1092-5528</orcidid><orcidid>https://orcid.org/0000-0001-7638-1610</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | 7Li NMR spectroscopy carbonyl alkylation cerium Chemistry Chemistry, Multidisciplinary Dominant species Inspection Ion pairs lithium Lithium chloride Low temperature Magnetic resonance spectroscopy n-butyl NMR NMR spectroscopy Nuclear magnetic resonance Physical Sciences Reagents Science & Technology Solvents |
| title | CeCl3/n‐BuLi: Unraveling Imamoto's Organocerium Reagent |
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