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Within the versatile synthetic toolbox, the semipinacol rearrangement (SPR) stands as one of the most powerful tools for assembling this sterically congested motif. In this context, \u200cradical\u2010mediated SPR pathways\u200c, especially those entailing alkyl migrations, remain underexplored from a strategic standpoint. Herein, we report a visible light\u2010promoted formal SPR of tertiary allyl alcohols using in situ\u2010generated triplet nitrene species as the initiator under redox\u2010neutral conditions. This method demonstrates broad substrate scope, enabling efficient construction of all\u2010carbon quaternary centers across various steric environments, including rigid cyclic\/spiro frameworks and flexible acyclic systems. Mechanistic investigations reveal substrate\u2010dependent pathways: alkenyl cyclobutanols undergo triplet nitrene addition followed by concurrent ring\u2010expansion and hydrogen atom transfer (HAT) to form cyclic ketones, while nonactivated allyl alcohols proceed through aziridination\/ring\u2010opening\/SPR sequences to produce linear \u03b2\u2010amino ketones. Preliminary biological assessments of these \u03b1\u2010quaternary \u03b2\u2010aminoketone derivatives revealed that compound\n                    <jats:bold>4a<\/jats:bold>\n                    exhibited potent anti\u2010DENV\u20102 activity, with an EC\n                    <jats:sub>50<\/jats:sub>\n                    value of 0.95\u00a0\u00b1\u00a00.02 \u00b5M against viral replication.\n                  <\/jats:p>","DOI":"10.1002\/anie.7133146","type":"journal-article","created":{"date-parts":[[2026,10,10]],"date-time":"2026-10-10T08:47:38Z","timestamp":1791622058000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Modular Construction of Cyclic and Linear Quaternary Carbon Centers through Visible\u2010Light\u2010Induced Triplet Nitrene Transfer 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