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. [ABSTRACT FROM AUTHOR]