Nickel-Catalyzed Adaptive Migration-Enabled Asymmetric Cross-Hydrocarbonylation of Unactivated Alkenes.

Transition-metal-catalyzed regio- and enantioselective cross-coupling of alkyl metallic species has emerged as a cornerstone in modern organic synthesis, which enables the construction of carbon-carbon and carbon-heteroatom bonds with high precision to facilitate rapid access to important organic targets with molecular complexity. However, the selective formation and utilization of different alkyl metallic intermediates from one precursor under identical conditions remain unknown and challenging. Herein, a Ni-catalyzed adaptive migratory asymmetric cross-hydroacylation of unactivated alkenes for the synthesis of enantioenriched α-arylated ketones has been developed. One alkene serves as a precursor for two different alkyl metallic intermediates by adaptive migration, providing one of the most straightforward pathways to access enantioenriched α-arylated ketones.