{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T22:50:17Z","timestamp":1790981417863,"version":"4.1.0"},"reference-count":85,"publisher":"Wiley","issue":"26","license":[{"start":{"date-parts":[[2022,5,5]],"date-time":"2022-05-05T00:00:00Z","timestamp":1651708800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001711","name":"Schweizerischer Nationalfonds zur F\u00f6rderung der Wissenschaftlichen Forschung","doi-asserted-by":"publisher","award":["188573"],"award-info":[{"award-number":["188573"]}],"id":[{"id":"10.13039\/501100001711","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2022,6,27]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Though LiTMP (TMP=2,2\u2032,6,6\u2032\u2010tetramethylpiperidide) is a commonly used amide, surprisingly the heavier NaTMP has hardly been utilised. Here, by mixing NaTMP with tridentate donor PMDETA (<jats:italic>N,N,N<\/jats:italic>\u2032<jats:italic>,N<\/jats:italic>\u2032\u2032<jats:italic>,N<\/jats:italic>\u2032\u2032\u2010pentamethyldiethylenetriamine), we provide structural, and mechanistic insights into the sodiation of non\u2010activated arenes (e.g. anisole and benzene). While these reactions are low yielding, adding B(O<jats:italic>i<\/jats:italic>Pr)<jats:sub>3<\/jats:sub> has a profound effect, not only by intercepting the C<jats:sub>Ar<\/jats:sub>\u2010Na bond, but also by driving the metalation reaction towards quantitative formation of more stabilized sodium aryl boronates. Demonstrating its metalating power, regioselective C2\u2010metalation\/borylation of naphthalene has been accomplished contrasting with single\u2010metal based protocols which are unselective and low yielding. Extension to other arenes allows for in situ generation of aryl boronates which can then directly engage in Suzuki\u2013Miyaura couplings, furnishing a range of biaryls in a selective and efficient manner.<\/jats:p>","DOI":"10.1002\/anie.202204262","type":"journal-article","created":{"date-parts":[[2022,4,14]],"date-time":"2022-04-14T09:11:41Z","timestamp":1649927501000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":40,"title":["Enhancing Metalating Efficiency of the Sodium Amide NaTMP in Arene Borylation Applications"],"prefix":"10.1002","volume":"61","author":[{"given":"Leonie J.","family":"Bole","sequence":"first","affiliation":[{"name":"Departement f\u00fcr Chemie, Biochemie und Pharmazie Universit\u00e4t Bern  Freiestrasse 3 3012 Bern Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2635-8030","authenticated-orcid":false,"given":"Andreu","family":"Tortajada","sequence":"additional","affiliation":[{"name":"Departement f\u00fcr Chemie, Biochemie und Pharmazie Universit\u00e4t Bern  Freiestrasse 3 3012 Bern Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3998-7506","authenticated-orcid":false,"given":"Eva","family":"Hevia","sequence":"additional","affiliation":[{"name":"Departement f\u00fcr Chemie, Biochemie und Pharmazie Universit\u00e4t Bern  Freiestrasse 3 3012 Bern Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,5,5]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527667512.ch1"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201301837"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201301837"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1055\/a-1478-7061"},{"key":"e_1_2_3_4_1","unstructured":"\u00a0"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020118)41:2<340::AID-ANIE340>3.0.CO;2-D"},{"key":"e_1_2_3_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020118)114:2<350::AID-ANGE350>3.0.CO;2-Y"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00104a001"},{"key":"e_1_2_3_7_2","first-page":"187","volume-title":"Advances in Heterocyclic Chemistry","author":"Queguiner 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was isolated as a pure solid from 1\u2009:\u20091 reaction ofnBuNa and TMP(H) in hexane see the Supporting Information for the further details. This method differs from the work reported by Takai where NaTMP is prepared in situ using a Na dispersion and then used for metalation of activated heteroarenes see reference\u2005[5a]."},{"key":"e_1_2_3_48_1","unstructured":"\u00a0"},{"key":"e_1_2_3_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.7b00549"},{"key":"e_1_2_3_50_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4SC01108B"},{"key":"e_1_2_3_51_2","unstructured":"See references\u2005[11a] and [14]."},{"key":"e_1_2_3_52_1","unstructured":"Selected references:"},{"key":"e_1_2_3_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo052400g"},{"key":"e_1_2_3_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol2016252"},{"key":"e_1_2_3_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol302063g"},{"key":"e_1_2_3_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b01681"},{"key":"e_1_2_3_57_2","unstructured":"see ref.\u2005[4] and [12a]."},{"key":"e_1_2_3_58_1","unstructured":"\u00a0"},{"key":"e_1_2_3_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00142a020"},{"key":"e_1_2_3_60_1","unstructured":"An equimolar mixture of NaTMP and B(OiPr)3in C6D12did not show the formation of any interaction as judged by11B NMR spectroscopy. Upon addition of PMDETA the formation of TMP(H) and the change in the signals of PMDETA in the1H NMR spectrum suggest its metalation.11B NMR shows a new signal at 4.45\u2005ppm consistent with a 4-coordinated B environment. Similar metalation of PMDETA has been seen in Trans Metal Trapping with LiTMP and Ga(CH2TMS)3: see ref.\u2005[11a]."},{"key":"e_1_2_3_61_1","unstructured":"\u00a0"},{"key":"e_1_2_3_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01262a005"},{"key":"e_1_2_3_63_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)87763-2"},{"key":"e_1_2_3_64_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT01118K"},{"key":"e_1_2_3_65_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC00670H"},{"key":"e_1_2_3_66_1","unstructured":"Selected examples:"},{"key":"e_1_2_3_67_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201500793"},{"key":"e_1_2_3_68_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201306884"},{"key":"e_1_2_3_68_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201306884"},{"key":"e_1_2_3_69_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202104275"},{"key":"e_1_2_3_69_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202104275"},{"key":"e_1_2_3_70_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900206p"},{"key":"e_1_2_3_71_1","unstructured":"\u00a0"},{"key":"e_1_2_3_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1108326"},{"key":"e_1_2_3_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b00400"},{"key":"e_1_2_3_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/om4007664"},{"key":"e_1_2_3_75_1","unstructured":"Deposition Numbers2159450 (for1\u22c5TMEDA) 2159451 (for2\u22c5(THF)3) 2159452 (for4) and 2159453 (for5)contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202204262","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202204262","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202204262","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,2,13]],"date-time":"2024-02-13T09:54:28Z","timestamp":1707818068000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202204262"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,5,5]]},"references-count":85,"journal-issue":{"issue":"26","published-print":{"date-parts":[[2022,6,27]]}},"alternative-id":["10.1002\/anie.202204262"],"URL":"https:\/\/doi.org\/10.1002\/anie.202204262","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,5,5]]},"assertion":[{"value":"2022-03-22","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-05-05","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202204262"}}