A General Access to Aryl‐Alkyl Ketones via Nickel‐Catalyzed Carbonylative Reductive Cross‐Coupling Reactions

Transition-metal-catalyzed carbonylation reactions have emerged as a versatile and powerful strategy for the production of diverse value-added carbonyl-containing compounds. Nevertheless, the carbonylative synthesis of alkyl ketones, particularly those incorporating secondary or tertiary alkyl fragments, remains underexplored and poses significant challenges. Herein, we present a nickel-catalyzed carbonylative reductive cross-coupling reaction to synthesize a wide range of aryl-alkyl ketones from readily available alkyl halides, aryl iodides, and Mo(CO)₆. This protocol exhibits excellent compatibility with primary, secondary, and tertiary alkyl electrophiles as well as aryl electrophiles bearing electron-withdrawing or electron-donating groups, offering a general access to aryl-alkyl ketones under mild conditions. Mechanistic studies reveal that Mo(CO)₆ not only serves as a safe and effective CO surrogate, but also plays a crucial role in facilitating the nickel carbonyl species, which is critical for promoting the selective synthesis of aryl-alkyl ketones.