Ligand Relay Catalysis Enables Asymmetric Migratory Reductive Acylation of Olefins or Alkyl Halides

Design of ligands in transition-metal
catalyzed reactions is challenging,
especially in asymmetric transformations. With each step in the catalytic
cycle promoted by its privileged ligand and different steps well-connected
by dynamic ligand exchange, synergistic combination of multiple ligands
could potentially enhance the catalytic efficiency and selectivity.
Now, this concept has been applied to the NiH-catalyzed asymmetric
remote hydroacylation of olefins and migratory acylation of alkyl
halides with excellent regio- and enantioselectivity, utilizing two
simple ligands, one for chain-walking and the other for asymmetric
acylation. Starting from abundant alkenes/alkyl halides and carboxylic
acids, a wide range of enantioenriched chiral α-aryl ketones
can be efficiently accessed under mild conditions.