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The direct interconversion of heterocyclic cores via skeletal editing provides rapid access to structurally diverse bioactive molecules. Herein, we report a Ru-catalyzed ring expansion strategy that converts isoxazoles into pyrimidines via O-to-CN transmutation. The transformation employs readily available nitriles as the CN source and proceeds via ruthenium-catalyzed N\u2013O bond cleavage to generate an enaminone intermediate, followed by nucleophilic addition and cyclization. This protocol accommodates a broad range of functional groups and enables the late-stage modification of complex pharmaceuticals, including receptor modulators and anticancer agents. This skeletal editing strategy expands the synthetic toolbox for medicinal chemistry and scaffold diversification.<\/jats:p>","DOI":"10.1021\/jacsau.6c00918","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T16:02:19Z","timestamp":1785945739000},"page":"4803-4810","source":"Crossref","is-referenced-by-count":0,"title":["Skeletal Editing\nof Isoxazoles to Pyrimidines via\nO-to-CN Transmutation"],"prefix":"10.1021","volume":"6","author":[{"given":"Lingqi","family":"Chen","sequence":"first","affiliation":[{"name":"Northwest University , , ,","place":["Xi\u2019an, P. R. China, 710069"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chenzhe","family":"Yun","sequence":"additional","affiliation":[{"name":"Northwest University , , ,","place":["Xi\u2019an, P. R. China, 710069"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yueyue","family":"Zhang","sequence":"additional","affiliation":[{"name":"Northwest University , , ,","place":["Xi\u2019an, P. R. China, 710069"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guoxiang","family":"Sun","sequence":"additional","affiliation":[{"name":"Northwest University , , ,","place":["Xi\u2019an, P. R. China, 710069"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3131-4558","authenticated-orcid":true,"given":"Hong","family":"Lu","sequence":"additional","affiliation":[{"name":"Northwest University , , ,","place":["Xi\u2019an, P. R. China, 710069"]},{"name":"NWU & Sinofuse , , ,","place":["Xi\u2019an, P. R. 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B.\n          Preparation of bis(hetero)aryl substituted\nisoxazoles for use as therapeutic neuronal nicotinic receptor modulators. WO Patent WO2009149135 A1, 2009."},{"key":"2026083023173608600_cit48","doi-asserted-by":"publisher","first-page":"141","DOI":"10.1007\/s11010-016-2777-z","article-title":"Induction\nof Apoptosis\nand Downregulation of ER\u03b1 in DMBA-induced mammary gland tumors\nin Sprague\u2013Dawley rats by synthetic 3,5-disubstituted isoxazole\nderivatives","volume":"420","author":"Ananda","year":"2016","journal-title":"Mol. Cell. Biochem."},{"key":"2026083023173608600_cit49","doi-asserted-by":"publisher","first-page":"4841","DOI":"10.1016\/j.bmc.2011.06.074","article-title":"Isoxazole\nsubstituted chromans against oxidative stress-induced\nneuronal damage","volume":"19","author":"Koufaki","year":"2011","journal-title":"Bioorg. Med. 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