Room-Temperature Decarboxylative Couplings of α-Oxocarboxylates with Aryl Halides by Merging Photoredox with Palladium Catalysis

Enabled by merging iridium photoredox catalysis and palladium catalysis, α‐oxocarboxylate salts can be decarboxylatively coupled with aryl halides to generate aromatic ketones and amides at room temperature. DFT calculations suggest that this reaction proceeds through a Pd0–PdII–PdIII pathway, in which the PdIII intermediate is responsible for reoxidizing IrII to complete the IrIII–*IrIII–IrII photoredox cycle. Like a mergin’: Enabled by merging iridium photoredox catalysis and palladium catalysis, palladium‐catalyzed decarboxylative coupling of α‐oxocarboxylates with aryl halides can proceed at room temperature. DFT calculations suggest that a Pd0–PdII–PdIII catalytic cycle is merged with an IrIII–*IrIII–IrII photoredox cycle, in which PdIII is responsible for oxidizing IrII to complete the photoredox cycle.