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However, nucleophilic functionalization at\n                    <jats:italic>meta\u2010<\/jats:italic>\n                    position of pyridines has remained elusive because of the intrinsic polarity mismatch. In this study, we report a mild and practical protocol for\n                    <jats:italic>meta<\/jats:italic>\n                    \u2010selective nucleophilic alkoxylation of azines using alcohols through a dearomatization\u2013rearomatization sequence. Taking advantage of oxazino\u2010pyridines as redox\u2010active intermediates, single\u2010electron oxidation generates the corresponding radical cations, which undergo nucleophilic addition to afford allylic radicals. Distinct from the established radical\u2013radical cross\u2010coupling pathway, these nucleophilic allylic radicals undergo further oxidation to form electrophilic allylic cations, thereby enabling capture by alcohols prior to rearomatization. This umpolung mechanism is supported by both experimental and computational studies. This catalyst\u2010free method features precise regiocontrol, remarkable functional group tolerance, scale\u2010up potential, and applicability to late\u2010stage functionalization of pharmaceuticals. Furthermore, this strategy was extended to nucleophilic\n                    <jats:italic>meta<\/jats:italic>\n                    \u2010hydroxylation of pyridines using water, as well as chlorination, bromination, and iodination using halide salts.\n                  <\/jats:p>","DOI":"10.1002\/anie.4582039","type":"journal-article","created":{"date-parts":[[2026,9,14]],"date-time":"2026-09-14T07:24:39Z","timestamp":1789370679000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Umpolung at the\n                    <i>meta<\/i>\n                    \u2010Positions of Oxazino\u2010Pyridines Enabling Nucleophilic Pyridine Functionalization"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-6648-9697","authenticated-orcid":false,"given":"Qixin","family":"Li","sequence":"first","affiliation":[{"name":"Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target &amp; Clinical 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