Rapid assembly of enantioenriched α-arylated ketones via Ni-catalyzed asymmetric cross-hydrocarbonylation enabled by alkene sorting.

Enantioenriched α-arylated dialkyl ketones with acidic proton are ubiquitous subunits in valuable target organic molecules and serve as versatile synthetic precursors for other value-added chiral blocks. Herein, a distinct synthetic strategy of enantioenriched α-arylated dialkyl ketones enabled by nickel-catalyzed iterative cross-hydrocarbonylation of two alkenes has been developed, representing a reaction mode for the direct synthesis of asymmetric α-arylated dialkyl ketones. One aliphatic alkene and one styrene are creatively used as surrogates of two different alkyl precursors. Two different alkenes are sewed together by a "carbonyl glue" with exclusive alkene sorting. This straightforward and gas-free protocol transforms a diverse array of styrene and unactivated alkenes into highly valuable α-arylated dialkyl ketones with high levels of enantioselectivity, allowing for the construction of enantioenriched unsymmetric dialkyl ketones from only alkenes. This process is also applicable to late-stage functionalization of complex molecules.