Palladium-Catalyzed Allylic Carbonylative Negishi Cross-Coupling Reactions with Sterically Bulky Aromatic Isocyanides

Herein, the palladium-catalyzed allylic carbonylative Negishi cross-coupling reaction employing sterically bulky aromatic isocyanides as the CO surrogate was disclosed.The leverage of sterically bulky aromatic isocyanide minimizes the side β-H elimination in carboxylation reaction, affords synthetically important β,γ-unsaturated ketones with high regioselectivity and stereoselectivity, thereby tackles the long-standing challenge in Pd-catalyzed allylic carbonylative cross-coupling with CO gas.Moreover, this protocol exhibits the advantage including mild reaction conditions, as well as broad substrate scope due to the utilization of Negishi reagent as the carbon nucleophiles.