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However, their use in <jats:italic>meta<\/jats:italic>-selective C\u2212H functionalizations remains a substantial unmet catalytic challenge. Herein, we report the ruthenium-catalyzed <jats:italic>meta<\/jats:italic>-C\u2013H alkylation of aromatic carboxylic acids with various functionalized alkyl halides. A bidentate <jats:italic>N<\/jats:italic>-ligand increases the electron density at the metal center of <jats:italic>ortho<\/jats:italic>-benzoate ruthenacycles to the extent that single-electron reductions of alkyl halides can take place. The subsequent addition of alkyl radicals is exclusively directed to the position <jats:italic>para<\/jats:italic> to the C<jats:sub>Ar<\/jats:sub>\u2013Ru bond, i.e., <jats:italic>meta<\/jats:italic> to the carboxylate group. The resulting catalytic <jats:italic>meta<\/jats:italic>-C\u2212H alkylation extends to a wide range of (hetero)aromatic carboxylic acids including benzofused five-membered ring heteroarenes but no pyridine derivatives in combination with secondary\/tertiary alkyl halides, including fluorinated derivatives. It also allows site-selective C5\u2212H alkylation of 1-naphthoic acids. The products are shown to be synthetic hubs en route to <jats:italic>meta<\/jats:italic>-alkylated aryl ketones, nitriles, amides, esters and other functionalized products.<\/jats:p>","DOI":"10.1038\/s41467-024-49362-2","type":"journal-article","created":{"date-parts":[[2024,7,2]],"date-time":"2024-07-02T13:02:52Z","timestamp":1719925372000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Ligand-enabled ruthenium-catalyzed meta-C\u2212H alkylation of (hetero)aromatic carboxylic acids"],"prefix":"10.1038","volume":"15","author":[{"given":"Xianglin","family":"Luo","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peichao","family":"Hou","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiayi","family":"Shen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yifeng","family":"Kuang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fengchao","family":"Sun","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4355-0294","authenticated-orcid":false,"given":"Huanfeng","family":"Jiang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2547-3037","authenticated-orcid":false,"given":"Lukas J.","family":"Goo\u00dfen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9450-9454","authenticated-orcid":false,"given":"Liangbin","family":"Huang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2024,7,2]]},"reference":[{"key":"49362_CR1","doi-asserted-by":"publisher","first-page":"1725","DOI":"10.1351\/pac200880081725","volume":"80","author":"LJ Goo\u00dfen","year":"2008","unstructured":"Goo\u00dfen, L. 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