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Carboxylic acids would be ideal precursors owing to their abundance and structural diversity, but their direct conversion into organoboron compounds remains elusive. This longstanding challenge stems from an intrinsic redox incompatibility between oxidative decarboxylation and conventional borylation chemistry. Here, we report a direct decarboxylative borylation of native carboxylic acids enabled by a radical-organometallic relay strategy. The reaction proceeds without substrate preactivation and is applicable to primary, secondary, and tertiary carboxylic acids, exhibiting broad functional group tolerance and enabling late-stage borylation of pharmaceuticals and peptides. By resolving a fundamental redox incompatibility, this work establishes a new reaction paradigm in which oxidative radical generation is directly integrated with organometallic C\u2013B bond formation.<\/jats:p>","DOI":"10.1021\/jacs.6c12595","type":"journal-article","created":{"date-parts":[[2026,8,23]],"date-time":"2026-08-23T15:23:32Z","timestamp":1787498612000},"page":"37310-37317","source":"Crossref","is-referenced-by-count":0,"title":["Direct Decarboxylative\nBorylation via Radical-Organometallic\nRelay"],"prefix":"10.1021","volume":"148","author":[{"given":"Chen","family":"Zhao","sequence":"first","affiliation":[{"name":"University of Chinese Academy of Sciences , , No.1 Yanqihu East Rd, Huairou District , ,","place":["Beijing, PR China, 101408"]},{"name":"University of Chinese Academy of Sciences , , No.1 Yanqihu East Rd, Huairou District , ,","place":["Beijing, PR China, 101408"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Meiyu","family":"Luo","sequence":"additional","affiliation":[{"name":"University of Chinese Academy of Sciences , , No.1 Yanqihu East Rd, Huairou District , ,","place":["Beijing, PR China, 101408"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Beibei","family":"Zhang","sequence":"additional","affiliation":[{"name":"University of Chinese Academy of Sciences , , No.1 Yanqihu East Rd, Huairou District , ,","place":["Beijing, PR China, 101408"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7448-6969","authenticated-orcid":true,"given":"Da","family":"Zhao","sequence":"additional","affiliation":[{"name":"University of Chinese Academy of Sciences , , No.1 Yanqihu East Rd, Huairou District , ,","place":["Beijing, PR China, 101408"]},{"name":"University of Chinese Academy of Sciences , , No.1 Yanqihu East Rd, Huairou District , ,","place":["Beijing, PR China, 101408"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,21]]},"reference":[{"key":"2026090312074892800_cit1","doi-asserted-by":"crossref","DOI":"10.1002\/9783527639328","volume-title":"Boronic\nAcids: Preparation and Applications in Organic Synthesis, Medicine\nand Materials","author":"Hall","year":"2011"},{"key":"2026090312074892800_cit2","doi-asserted-by":"publisher","first-page":"6722","DOI":"10.1002\/anie.201101379","article-title":"Cross-coupling\nreactions of organoboranes: an easy way to construct C\u2013C bonds\n(Nobel Lecture)","volume":"50","author":"Suzuki","year":"2011","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090312074892800_cit3","first-page":"39","volume-title":"Synthesis\nand Applications of Organoboron Compounds. Topics in Organometallic\nChemistry","author":"Ferna\u0301ndez","year":"2015"},{"key":"2026090312074892800_cit4","doi-asserted-by":"publisher","first-page":"5481","DOI":"10.1039\/C7CC01254C","article-title":"Stereospecific functionalizations\nand transformations\nof secondary and tertiary boronic esters","volume":"53","author":"Sandford","year":"2017","journal-title":"Chem.\nCommun."},{"key":"2026090312074892800_cit5","doi-asserted-by":"publisher","first-page":"12491","DOI":"10.1021\/acs.chemrev.9b00491","article-title":"Mechanistic development\nand recent applications of the Chan-Lam amination","volume":"119","author":"West","year":"2019","journal-title":"Chem. 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China Chem."},{"key":"2026090312074892800_cit39","doi-asserted-by":"publisher","first-page":"4749","DOI":"10.1039\/D1DT04276A","article-title":"Ligand properties of boryl ligands\nin bis-boryl rhodium(III)\ncomplexes: a case study","volume":"51","author":"Drescher","year":"2022","journal-title":"Dalton Trans."},{"key":"2026090312074892800_cit40","doi-asserted-by":"publisher","first-page":"99","DOI":"10.1021\/cr60324a001","article-title":"Mechanism\nof the thermal and photochemical decomposition of azoalkanes","volume":"80","author":"Engel","year":"1980","journal-title":"Chem. Rev."},{"key":"2026090312074892800_cit41","doi-asserted-by":"publisher","first-page":"1812","DOI":"10.1021\/acscentsci.5c01091","article-title":"Bimolecular homolytic\nsubstitution (SH2)\nand radical ligand transfer (RLT): emerging paradigms in radical transformations","volume":"11","author":"Fernandes","year":"2025","journal-title":"ACS Cent. 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Chem.\nSoc."},{"key":"2026090312074892800_cit50","doi-asserted-by":"publisher","first-page":"4621","DOI":"10.1021\/ja005872f","article-title":"Observation\nof unusual kinetics in\nHeck reactions of aryl halides: the role of non-steady-state catalyst\nconcentration","volume":"123","author":"Rosner","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312074892800_cit51","doi-asserted-by":"crossref","first-page":"1848","DOI":"10.1021\/ja003191e","article-title":"Kinetic\nstudies of Heck coupling reactions using palladacycle catalysts: experimental\nand kinetic modeling of the role of dimer species","volume":"123","author":"Rosner","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312074892800_cit52","doi-asserted-by":"publisher","first-page":"3657","DOI":"10.1021\/acscatal.9b00081","article-title":"Dehydropolymerization of H3B\u2022NMeH2 using a [Rh(DPEphos)]+ catalyst: the promoting\neffect of NMeH2","volume":"9","author":"Adams","year":"2019","journal-title":"ACS Catal."},{"key":"2026090312074892800_cit53","doi-asserted-by":"publisher","first-page":"19632","DOI":"10.1021\/jacs.5c01554","article-title":"Nickel-mediated\nradical\ncapture: evidence for a concerted inner-sphere mechanism","volume":"147","author":"Spielvogel","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026090312074892800_cit54","doi-asserted-by":"publisher","first-page":"7480","DOI":"10.1002\/chem.201500110","article-title":"Computational insight\ninto nickel-catalyzed carbon\u2013carbon versus carbon\u2013boron\ncoupling reactions of primary, secondary, and tertiary alkyl bromides","volume":"21","author":"Cheung","year":"2015","journal-title":"Chem. - Eur. J."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c12595","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/34\/37310\/67044741\/jacs.6c12595.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/34\/37310\/67044741\/jacs.6c12595.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T16:20:17Z","timestamp":1788452417000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/34\/37310\/5291658\/Direct-Decarboxylative-Borylation-via-Radical"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,21]]},"references-count":54,"journal-issue":{"issue":"34","published-online":{"date-parts":[[2026,8,21]]},"published-print":{"date-parts":[[2026,9,2]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c12595","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,21]]}}}