Axially Chiral Bridged Biaryls by Ni-Catalyzed Kinetic Asymmetric C–O Bond Cleavage

Axially chiral bridged biaryls represent an important
subset of
axially chiral biaryl scaffolds in fields ranging from organic synthesis
to biochemistry to materials science. While numerous catalytic strategies
have been elucidated for the construction of axial chirality, the
catalytic synthesis of axially chiral bridged biaryls in the enantioenriched
form remains underdeveloped. Herein, we demonstrate an approach to
synthesize diverse axially chiral bridged biaryls through nickel-catalyzed
kinetic asymmetric cleavage of the unactivated aromatic C–O
bond. The catalytic system features mild reaction conditions, high
resolution efficiency, and versatile post-functionalizations. Mechanistic
studies reveal the impact of the nickel catalyst’s chirality
on the stereochemical output of this transformation.