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Here we report a palladium\u2010catalyzed fluoroallylic alkylation of secondary nitroalkanes with\n                    <jats:italic>gem<\/jats:italic>\n                    \u2010difluorocyclopropanes that overturns this long standing reactivity paradigm by enabling their engagement through an inner\u2010sphere pathway. This strategy enables the switchable regiodivergence between linear and branched allylic nitroalkanes\u2014an outcome unattainable under classical Tsuji\u2013Trost conditions and unprecedented for secondary nitroalkanes. This method exhibits excellent functional\u2010group and heterocycle tolerance and is readily applicable to the late\u2010stage modification of structurally complex bioactive molecules. Moreover, its synthetic utility has been further highlighted by various downstream derivatizations of the resulting 2\u2010fluoroallylic\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010tertiary nitroalkanes. DFT studies indicate that ligand\u2010controlled oxygen coordination to electrophilic fluoro\u2010\u03c0\u2010allyl\u2013Pd intermediates enables an inner\u2010sphere 3,3'\u2010reductive elimination, thereby accounting for the excellent regioselectivity in C(sp\n                    <jats:sup>3<\/jats:sup>\n                    )\u2013C(sp\n                    <jats:sup>3<\/jats:sup>\n                    ) bond formation.\n                  <\/jats:p>","DOI":"10.1002\/anie.7706265","type":"journal-article","created":{"date-parts":[[2026,4,17]],"date-time":"2026-04-17T05:39:54Z","timestamp":1776404394000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Ligand\u2010Switched Regiodivergent Fluoroallylic Alkylation of Secondary Nitroalkanes via an Unusual Inner\u2010Sphere Pathway"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1668-4422","authenticated-orcid":false,"given":"Lin","family":"Yu","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development Guangxi University  Nanning Guangxi P. 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