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Adv."],"published-print":{"date-parts":[[2026,7,10]]},"abstract":"<jats:p>Radical phosphonylation has traditionally relied on single-electron transfer mechanisms. In contrast, strategies using energy-transfer pathways to enable scaffold rearrangement are rare. Here, we report an energy transfer catalysis strategy that diverts reactivity toward a previously unexplored pathway: a direct photochemical diradical rearrangement between homoallylic alcohols and phosphorus(III) reagents. Mechanistic studies, supported by computational calculation, provide definitive support for an energy-transfer\u2013mediated diradical mechanism. This operationally simple and mild process, driven by visible light, forges strained phosphorylated cyclopropanes with high efficiency via diradical intermediates that undergo radical addition to phosphorus, \u03b2-scission, and recombination. With broad substrate compatibility and excellent functional group tolerance, this method delivers diverse three-membered rings containing phosphine oxide in good to excellent yields. This work establishes a new reaction manifold for organophosphorus synthesis, demonstrating how energy transfer catalysis can redirect traditional reactivity to access valuable strained architectures through previously inaccessible rearrangement pathways.<\/jats:p>","DOI":"10.1126\/sciadv.aee4031","type":"journal-article","created":{"date-parts":[[2026,7,8]],"date-time":"2026-07-08T18:00:55Z","timestamp":1783533655000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":2,"title":["Redirecting radical phosphonylation via energy-transfer\u2013enabled diradical rearrangement"],"prefix":"10.1126","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-4280-0368","authenticated-orcid":true,"given":"Kai-Dian","family":"Li","sequence":"first","affiliation":[{"name":"School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, 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