Nickel-catalyzed hydrobivinylation of enones with 1,3-dienes

Leveraging the power of organometallic chemistry for inventing diverse functionalization of dienes is of great significance in synthetic chemistry. The coupling of dienes with ct,0-unsaturated ketones generally affords dehydroallylated products under low-valent metal catalysis. Therefore, it is highly appealing to exploit an efficient catalytic system to achieve a distinct chemoselectivity, especially with switchable regioselectivity. Through tuning the oxidative cyclometallation step, we herein report a nickel(0)-catalyzed regiodivergent hydrobivinylation of enones with dienes. Aryldienes participate in the transformation efficiently, providing 1,4-disubstituted dienes in good regio-and stereoselectivity. By contrast, the addition site switches to the C1 position in the case of alkyldienes. The key to this strategy's success depends on the preferential formation of oxanickelacycle. Besides, the resulting diene products could undergo an array of elaborate transformations, which highlights the potential of this protocol.