A ligand-controlled switchable nickel-catalyzed coupling reaction between nitriles and aryl triflates has been developed, enabling the divergent synthesis of two privileged classes of molecules—ketones and diarylmethanes—from identical starting materials. The chemoselectivity is mainly dictated by the choice of phosphine ligand: employing dppp as the ligand promotes reductive addition/hydrolysis, yielding ketones, while switching to Xantphos directs the pathway toward decya-native cross-coupling to furnish diarylmethanes. This protocol features broad substrate scope (up to 60 examples), excellent functional group tolerance, and high chemoselectivity, thus providing a versatile and stepeconomical strategy for modular synthesis of ketones and diarylmethanes from readily available nitriles.

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