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Herein, we present a ligand\u2010centered redox\u2010controlled effective strategy employing a zinc amide catalyst (\n                    <jats:bold>C<\/jats:bold>\n                    ) to achieve facile defluoroamination of fluoroarenes with several N\u2010nucleophiles (&gt;90 substrates) under mild conditions. Notably, this adaptable protocol works readily with most types of fluoroarenes and a diverse range of N\u2500H moieties that include secondary and primary amines, indoles, azoles, and\u00a0amides under the same reaction conditions and encouragingly offers excellent functional group compatibility. Intriguingly, we also demonstrated its application in one\u2010pot synthesis of (un)symmetrical triaryl amines from primary amine itself and the selective activation of C\u2500F bonds to access F\u2010containing amines, relevant to drug synthesis. Finally, detailed mechanistic probes via active\u2010intermediate\u2010capture, EPR analysis, and various control experiments indicate that the reaction proceeds through a radical\u2010mediated C\u2500N coupling pathway. Importantly, use of Zn(II) center as a template to hold the two amide moieties together in\n                    <jats:bold>C<\/jats:bold>\n                    enables facile intramolecular electron transfer to generate the radical intermediates for the present protocol. Finally, the practical utility of this methodology was\u00a0showcased by synthesizing various drug derivatives.\n                  <\/jats:p>","DOI":"10.1002\/anie.202504156","type":"journal-article","created":{"date-parts":[[2025,4,16]],"date-time":"2025-04-16T04:36:11Z","timestamp":1744778171000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Adaptive Defluoroamination of Aryl Fluorides: Harnessing the Catalytic Potential of a Unique Zinc Amide Compound"],"prefix":"10.1002","volume":"64","author":[{"given":"Sangita","family":"Sahoo","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Madras  Chennai 600036 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arnab","family":"Rit","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Madras  Chennai 600036 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