Ni-catalyzed adaptive migration: Asymmetric cross-hydrocarbonylation of unactivated alkenes to access enantioenriched α-arylated ketones

Transition-metal catalyzed regio-and enantioselective crosscoupling of alkyl metallic species has emerged as a cornerstone in modern organic synthesis, which enables the highly precise formation of carbon-carbon and carbon-heteroatom bonds, thereby facilitating the efficient synthesis of structurally complex and functionally important organic molecules. However, the selective generation and application of diverse alkyl metal intermediates from a single precursor under identical reaction conditions remains unexplored and represents an unsolved challenge. Herein, a new reaction mode enabled by nickelcatalyzed adaptive migration of one alkyl metallic intermediate to form both thermodynamic and kinetic favored alkyl metallic intermediates has been established, which could undergo asymmetric crosshydrocarbonylation to synthesize enantioenriched α-arylated ketones. This strategy enables an identical alkene serves as the precursor for two distinct alkyl metal intermediates through adaptive migration, offering one of the most direct and efficient approaches to access enantioenriched α-arylated ketones. Moreover, the adaptive migration strategy could be applied to two different alkenes. Alkene sorting enables one alkene corresponds to generate thermodynamic favored alkyl nickel intermediate, while the other alkene corresponds to generate kinetic favored alkyl nickel intermediate.

Publikationsverlauf

Eingereicht: 14. September 2025

Angenommen nach Revision: 13. Oktober 2025

Accepted Manuscript online:
13. Oktober 2025