Visible Light‐Induced Pd Catalysis

<jats:title>Abstract</jats:title> <jats:p>Over the past decade, visible light activation has transformed palladium catalysis by enabling reactivity patterns that are inaccessible under purely thermal conditions. Whereas early photocatalytic strategies relied on discrete photosensitizers or dual photoredox manifolds, a distinct paradigm has emerged in which palladium itself serves as both the light‐absorbing species and the catalytic center. Photoexcitation of palladium complexes directly perturbs the conventional two‐electron organometallic pathways, diverting them into single‐electron manifolds, thus giving rise to hybrid Pd‐radical intermediates. More specifically, phosphine‐ligated Pd(0) complexes exemplify this behavior, enabling mild generation of aryl and alkyl radicals and unlocking diverse transformations, including desaturation reactions, alkyl‐Heck‐type processes, multicomponent alkene functionalizations, and asymmetric CH amination. More recent studies have further revealed excitation‐enabled modulation of PdH reactivity, establishing hydricity regimes distinct from the ground‐state behavior and allowing access to electron‐deficient alkenes and unconventional radical precursors. This chapter surveys the evolution of visible light‐induced palladium catalysis, emphasizing reaction classes and mechanistic principles that define this rapidly advancing field.</jats:p>