A novel, selective and high-yielding palladium-catalyzed carbonylative arylation of a variety of weakly acidic (pKa 25–43 in DMSO) benzylic and heterobenzylic C(sp3)−H bonds with aryl bromides has been achieved. This system is applicable to a range of nucleophiles for access to sterically and electronically diverse α-aryl or α,α-diaryl ketones, which are ubiquitous substructures in biologically active compounds. A PdL2-based catalyst was identified as the most efficient and selective by high-throughput experimentation (HTE), enabling carbonylative arylation with aryl bromides under 1 atm CO to provide the ketone products without the formation of direct coupling byproducts. The scope and mechanism will be discussed.

Palladium-catalyzed benzylic C(sp3)–H carbonylative arylation with aryl bromides

ACS Spring 2022

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