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.
