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To address this, selective arylation of sp\n                    <jats:sup>3<\/jats:sup>\n                    C\u2212H bonds in amides and alcohols has been achieved using divalent palladium as an excited\u2010state transition metal (TM) species at room temperature. Our approach unveils a non\u2010redox\u2010neutral pathway to achieve C(sp\n                    <jats:sup>3<\/jats:sup>\n                    )\u2013C(sp\n                    <jats:sup>2<\/jats:sup>\n                    ) cross\u2010couplings, utilizing aryl iodides as both hydrogen atom transfer (HAT) and arylating agents for the first time under Pd\u2010photochemical conditions. The mechanism involves photo\u2010induced Pd(II)\u2010catalyzed aryl radical generation, HAT, and aryl migration, effectively bypassing the common\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010hydride elimination and annulation pathways. Mechanistic investigations using isotope\u2010labeled compounds and density functional theory (DFT) studies support the mechanistic rationale, affirming both the feasibility and intricacies of this effective transformation.\n                  <\/jats:p>","DOI":"10.1002\/anie.202522979","type":"journal-article","created":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T09:49:15Z","timestamp":1762768155000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Bypassing \u03b2\u2010Hydride Elimination: Excited\u2010State Pd\u2010Catalyzed C(sp\n                    <sup>3<\/sup>\n                    )\u2013C(sp\n                    <sup>2<\/sup>\n                    ) Coupling at Room Temperature"],"prefix":"10.1002","volume":"65","author":[{"given":"Kuntal","family":"Pal","sequence":"first","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  Thuwal 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