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.

Automated summary

Leveraging the power of organometallic chemistry, this study presents a regiodivergent hydrobivinylation of enones with dienes catalyzed by nickel(0). Aryldienes efficiently participate in the reaction, providing 1,4-disubstituted dienes with good regio- and stereoselectivity, while the addition site shifts to the C1 position in the case of alkyldienes. The preferential formation of oxanickelacycle is crucial for the success of this strategy. Furthermore, the resulting diene products can undergo a variety of complex transformations, highlighting the potential of this protocol.