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This strategy enables the first oxidative coupling protocol of \u03b1,\u03b1\u2010difluorobenzylic C\u2500H bonds with heteronucleophiles. Here, transiently generated \u03b1,\u03b1\u2010difluorobenzylic carbanionic intermediates undergo halogen transfer from 2\u2010bromothiophenes to form electrophilic ArCF<jats:sub>2<\/jats:sub>Br compounds for in situ nucleophilic substitution, thereby avoiding \u03b1\u2010fluoride elimination pathways that typically plague \u03b1\u2010fluorocarbanions. This method streamlines the modular synthesis of \u03b1,\u03b1\u2010difluorobenzyl(thio)ethers and led to the broader realization that halogen transfer to unstable carbanions is an enabling principle across diverse C(sp<jats:sup>2<\/jats:sup>)\u2500H and C(sp<jats:sup>3<\/jats:sup>)\u2500H systems.<\/jats:p>","DOI":"10.1002\/anie.202502894","type":"journal-article","created":{"date-parts":[[2025,3,18]],"date-time":"2025-03-18T00:49:08Z","timestamp":1742258948000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Capturing Unstable Carbanionic Intermediates via Halogen Transfer: Base\u2010Promoted Oxidative Coupling Reactions of \u03b1,\u03b1\u2010Difluoromethylarenes"],"prefix":"10.1002","volume":"64","author":[{"given":"Leidy V.","family":"Hooker","sequence":"first","affiliation":[{"name":"Department of Chemistry Colorado State University  Fort Collins CO 80523 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The use of this protocol to access compounds that possess deoxyfluorination\u2010prone functional groups is experimentally demonstrated in the Supporting Information."},{"key":"e_1_2_6_97_1","unstructured":"See the Supporting Information for a discussion and an illustration of how traditional radical\u2010based C\u2500H bromination methods selectively functionalize methyl groups in compounds that contain both \u2500CH3and \u2500CF2H aryl substituents."},{"key":"e_1_2_6_98_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-2008-1032094"},{"key":"e_1_2_6_99_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0032-1316853"},{"key":"e_1_2_6_100_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0037-1610340"},{"key":"e_1_2_6_101_1","unstructured":"We found that compound26 derived from relatively acidic2 could be prepared using AbbVie's LiHMDS\/Br2halogenation method (Ref. 74) as described in the Supporting Information."},{"key":"e_1_2_6_102_1","unstructured":"For example the conditions shown in Figure 6a without PMPOH (1) present results in 45% mass balance of the ArCF2H (2) starting material after 5\u00a0min with less than 5% of the ArCF2Br (26) intermediate observed; see Supporting Information for details."},{"key":"e_1_2_6_103_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr941141k"},{"key":"e_1_2_6_104_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202301851"},{"key":"e_1_2_6_105_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00004a067"},{"key":"e_1_2_6_106_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00194a030"},{"key":"e_1_2_6_107_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.6b02550"},{"key":"e_1_2_6_108_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC02689A"},{"key":"e_1_2_6_109_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c13520"},{"key":"e_1_2_6_110_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-1991-20650"},{"key":"e_1_2_6_111_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-4-431-54186-8"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202502894","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,9,22]],"date-time":"2025-09-22T07:59:34Z","timestamp":1758527974000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202502894"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,4,14]]},"references-count":111,"journal-issue":{"issue":"21","published-print":{"date-parts":[[2025,5,19]]}},"alternative-id":["10.1002\/anie.202502894"],"URL":"https:\/\/doi.org\/10.1002\/anie.202502894","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,4,14]]},"assertion":[{"value":"2025-02-04","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-03-10","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-04-14","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202502894"}}