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 beta-H elimination in carboxylation reaction, affords synthetically important beta,gamma-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.

Automated summary

This study demonstrates the palladium-catalyzed allylic carbonylative Negishi cross-coupling reaction using sterically bulky aromatic isocyanides as a CO surrogate, leading to β,γ-unsaturated ketones with high regioselectivity and stereoselectivity. The advantages of this method include mild reaction conditions and a wide substrate scope due to the utilization of Negishi reagents as carbon nucleophiles.