Deoxygenative Difunctionalization of Aldehydes via Ketyl Radical and Light/Dark Pd Synergy

Abstract The direct deoxygenative difunctionalization of aldehydes offers a powerful yet underdeveloped strategy to convert abundant carbonyl feedstocks into structurally complex molecules. Here we report a visible‐light‐driven, redox‐neutral platform that merges ketyl radical generation from α‐acyloxy halides with hybrid Pd catalysis. This strategy enables aldehydes to serve as versatile C 1 synthons, delivering allylic sulfones in the presence of nucleophiles and conjugated dienes in their absence. The method exhibits broad scope across diverse vinylarenes, aldehydes, and sulfonyl partners, including late‐stage functionalization of natural products and pharmaceuticals. The synthetic utility of the products is highlighted through gram‐scale reactions, regioselective S N 2′ substitutions to construct quaternary carbon centers, and a one‐pot reductive hydrovinylation sequence. By bridging ketyl radical chemistry with hybrid Pd catalysis, this work establishes aldehyde deoxygenative difunctionalization as a new and practical entry to complex molecular architectures.