Ruthenium-Catalyzed Regiospecific Borylation of Methyl C−H Bonds
We report the regiospecific, ruthenium-catalyzed borylation of saturated terminal C−H bonds. Alkylboronates were obtained in 78−98% yields. The borylations of alkanes, trialkylamines, protected alcohols, and fluoroalkanes occurred regiospecifically at the methyl group that is least sterically hinder...
Gespeichert in:
| Veröffentlicht in: | Journal of the American Chemical Society 2006-10, Vol.128 (42), p.13684-13685 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 13685 |
|---|---|
| container_issue | 42 |
| container_start_page | 13684 |
| container_title | Journal of the American Chemical Society |
| container_volume | 128 |
| creator | Murphy, Jaclyn M Lawrence, Joshua D Kawamura, Kazumori Incarvito, Christopher Hartwig, John F |
| description | We report the regiospecific, ruthenium-catalyzed borylation of saturated terminal C−H bonds. Alkylboronates were obtained in 78−98% yields. The borylations of alkanes, trialkylamines, protected alcohols, and fluoroalkanes occurred regiospecifically at the methyl group that is least sterically hindered. In contrast to most organometallic C−H activation, the reactions of alkanes occurred in higher yields than the reactions of arenes. Reactions were conducted that probed steric and electronic effects on the alkyl borylation. These reactions showed that the borylation occurred preferentially at the methyl group that is least sterically hindered and most electron-deficient. Ruthenium compounds containing boryl ligands were synthesized, and one was characterized by X-ray crystallography. One of these compounds contained a rare bridging boryl ligand and served as a catalyst precursor for the borylation of octane. |
| doi_str_mv | 10.1021/ja064092p |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_68964292</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>68964292</sourcerecordid><originalsourceid>FETCH-LOGICAL-a447t-20f9cadc9be14b0e8fa88dda1c497ab2491580455ac922fcf2ba1c4e62a403993</originalsourceid><addsrcrecordid>eNpt0MtKxDAYBeAgio6XhS8g3Si4qCZpmiZLp6gjKIoXXIa_aaIZO-2YtOD4BK59RJ_EDjM4G1fh53wcwkFon-ATgik5HQPmDEs6XUMDklIcp4TydTTAGNM4EzzZQtshjPuTUUE20RbJMGNcpAM0vO_aV1O7bhLn0EI1-zRldG9eXBOmRjvrdDRs_KyC1jV11NjoxrSvsyrKf76-R31Ul2EXbViogtlbvjvo6eL8MR_F17eXV_nZdQyMZW1MsZUaSi0LQ1iBjbAgRFkC0UxmUFAmSSowS1PQklKrLS3mmeEUGE6kTHbQ0aJ36pv3zoRWTVzQpqqgNk0XFBeSMyppD48XUPsmBG-smno3AT9TBKv5YOpvsN4eLEu7YmLKlVwu1IPDJYCgobIeau3CyglKMp6w3sUL50JrPv5y8G-KZ0mWqse7ByUvn--eBclUvuoFHdS46Xzdb_fPB38B_9mOLw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>68964292</pqid></control><display><type>article</type><title>Ruthenium-Catalyzed Regiospecific Borylation of Methyl C−H Bonds</title><source>MEDLINE</source><source>American Chemical Society Journals</source><creator>Murphy, Jaclyn M ; Lawrence, Joshua D ; Kawamura, Kazumori ; Incarvito, Christopher ; Hartwig, John F</creator><creatorcontrib>Murphy, Jaclyn M ; Lawrence, Joshua D ; Kawamura, Kazumori ; Incarvito, Christopher ; Hartwig, John F</creatorcontrib><description>We report the regiospecific, ruthenium-catalyzed borylation of saturated terminal C−H bonds. Alkylboronates were obtained in 78−98% yields. The borylations of alkanes, trialkylamines, protected alcohols, and fluoroalkanes occurred regiospecifically at the methyl group that is least sterically hindered. In contrast to most organometallic C−H activation, the reactions of alkanes occurred in higher yields than the reactions of arenes. Reactions were conducted that probed steric and electronic effects on the alkyl borylation. These reactions showed that the borylation occurred preferentially at the methyl group that is least sterically hindered and most electron-deficient. Ruthenium compounds containing boryl ligands were synthesized, and one was characterized by X-ray crystallography. One of these compounds contained a rare bridging boryl ligand and served as a catalyst precursor for the borylation of octane.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja064092p</identifier><identifier>PMID: 17044685</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Boron Compounds - chemical synthesis ; Carbon - chemistry ; Catalysis ; Chemistry ; Exact sciences and technology ; General and physical chemistry ; Hydrogen - chemistry ; Methane - analogs & derivatives ; Models, Chemical ; Organometallic Compounds - chemical synthesis ; Ruthenium - chemistry</subject><ispartof>Journal of the American Chemical Society, 2006-10, Vol.128 (42), p.13684-13685</ispartof><rights>Copyright © 2006 American Chemical Society</rights><rights>2007 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a447t-20f9cadc9be14b0e8fa88dda1c497ab2491580455ac922fcf2ba1c4e62a403993</citedby><cites>FETCH-LOGICAL-a447t-20f9cadc9be14b0e8fa88dda1c497ab2491580455ac922fcf2ba1c4e62a403993</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/ja064092p$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja064092p$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=18217634$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/17044685$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Murphy, Jaclyn M</creatorcontrib><creatorcontrib>Lawrence, Joshua D</creatorcontrib><creatorcontrib>Kawamura, Kazumori</creatorcontrib><creatorcontrib>Incarvito, Christopher</creatorcontrib><creatorcontrib>Hartwig, John F</creatorcontrib><title>Ruthenium-Catalyzed Regiospecific Borylation of Methyl C−H Bonds</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>We report the regiospecific, ruthenium-catalyzed borylation of saturated terminal C−H bonds. Alkylboronates were obtained in 78−98% yields. The borylations of alkanes, trialkylamines, protected alcohols, and fluoroalkanes occurred regiospecifically at the methyl group that is least sterically hindered. In contrast to most organometallic C−H activation, the reactions of alkanes occurred in higher yields than the reactions of arenes. Reactions were conducted that probed steric and electronic effects on the alkyl borylation. These reactions showed that the borylation occurred preferentially at the methyl group that is least sterically hindered and most electron-deficient. Ruthenium compounds containing boryl ligands were synthesized, and one was characterized by X-ray crystallography. One of these compounds contained a rare bridging boryl ligand and served as a catalyst precursor for the borylation of octane.</description><subject>Boron Compounds - chemical synthesis</subject><subject>Carbon - chemistry</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Hydrogen - chemistry</subject><subject>Methane - analogs & derivatives</subject><subject>Models, Chemical</subject><subject>Organometallic Compounds - chemical synthesis</subject><subject>Ruthenium - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0MtKxDAYBeAgio6XhS8g3Si4qCZpmiZLp6gjKIoXXIa_aaIZO-2YtOD4BK59RJ_EDjM4G1fh53wcwkFon-ATgik5HQPmDEs6XUMDklIcp4TydTTAGNM4EzzZQtshjPuTUUE20RbJMGNcpAM0vO_aV1O7bhLn0EI1-zRldG9eXBOmRjvrdDRs_KyC1jV11NjoxrSvsyrKf76-R31Ul2EXbViogtlbvjvo6eL8MR_F17eXV_nZdQyMZW1MsZUaSi0LQ1iBjbAgRFkC0UxmUFAmSSowS1PQklKrLS3mmeEUGE6kTHbQ0aJ36pv3zoRWTVzQpqqgNk0XFBeSMyppD48XUPsmBG-smno3AT9TBKv5YOpvsN4eLEu7YmLKlVwu1IPDJYCgobIeau3CyglKMp6w3sUL50JrPv5y8G-KZ0mWqse7ByUvn--eBclUvuoFHdS46Xzdb_fPB38B_9mOLw</recordid><startdate>20061025</startdate><enddate>20061025</enddate><creator>Murphy, Jaclyn M</creator><creator>Lawrence, Joshua D</creator><creator>Kawamura, Kazumori</creator><creator>Incarvito, Christopher</creator><creator>Hartwig, John F</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>20061025</creationdate><title>Ruthenium-Catalyzed Regiospecific Borylation of Methyl C−H Bonds</title><author>Murphy, Jaclyn M ; Lawrence, Joshua D ; Kawamura, Kazumori ; Incarvito, Christopher ; Hartwig, John F</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a447t-20f9cadc9be14b0e8fa88dda1c497ab2491580455ac922fcf2ba1c4e62a403993</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><topic>Boron Compounds - chemical synthesis</topic><topic>Carbon - chemistry</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Hydrogen - chemistry</topic><topic>Methane - analogs & derivatives</topic><topic>Models, Chemical</topic><topic>Organometallic Compounds - chemical synthesis</topic><topic>Ruthenium - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Murphy, Jaclyn M</creatorcontrib><creatorcontrib>Lawrence, Joshua D</creatorcontrib><creatorcontrib>Kawamura, Kazumori</creatorcontrib><creatorcontrib>Incarvito, Christopher</creatorcontrib><creatorcontrib>Hartwig, John F</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 the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Murphy, Jaclyn M</au><au>Lawrence, Joshua D</au><au>Kawamura, Kazumori</au><au>Incarvito, Christopher</au><au>Hartwig, John F</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ruthenium-Catalyzed Regiospecific Borylation of Methyl C−H Bonds</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2006-10-25</date><risdate>2006</risdate><volume>128</volume><issue>42</issue><spage>13684</spage><epage>13685</epage><pages>13684-13685</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>We report the regiospecific, ruthenium-catalyzed borylation of saturated terminal C−H bonds. Alkylboronates were obtained in 78−98% yields. The borylations of alkanes, trialkylamines, protected alcohols, and fluoroalkanes occurred regiospecifically at the methyl group that is least sterically hindered. In contrast to most organometallic C−H activation, the reactions of alkanes occurred in higher yields than the reactions of arenes. Reactions were conducted that probed steric and electronic effects on the alkyl borylation. These reactions showed that the borylation occurred preferentially at the methyl group that is least sterically hindered and most electron-deficient. Ruthenium compounds containing boryl ligands were synthesized, and one was characterized by X-ray crystallography. One of these compounds contained a rare bridging boryl ligand and served as a catalyst precursor for the borylation of octane.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>17044685</pmid><doi>10.1021/ja064092p</doi><tpages>2</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2006-10, Vol.128 (42), p.13684-13685 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_68964292 |
| source | MEDLINE; American Chemical Society Journals |
| subjects | Boron Compounds - chemical synthesis Carbon - chemistry Catalysis Chemistry Exact sciences and technology General and physical chemistry Hydrogen - chemistry Methane - analogs & derivatives Models, Chemical Organometallic Compounds - chemical synthesis Ruthenium - chemistry |
| title | Ruthenium-Catalyzed Regiospecific Borylation of Methyl C−H Bonds |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-23T18%3A20%3A52IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Ruthenium-Catalyzed%20Regiospecific%20Borylation%20of%20Methyl%20C%E2%88%92H%20Bonds&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Murphy,%20Jaclyn%20M&rft.date=2006-10-25&rft.volume=128&rft.issue=42&rft.spage=13684&rft.epage=13685&rft.pages=13684-13685&rft.issn=0002-7863&rft.eissn=1520-5126&rft.coden=JACSAT&rft_id=info:doi/10.1021/ja064092p&rft_dat=%3Cproquest_cross%3E68964292%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=68964292&rft_id=info:pmid/17044685&rfr_iscdi=true |