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

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 C₁ 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_N2' 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.