Enantioselective Nickel-Catalyzed Mizoroki–Heck Cyclizations To Generate Quaternary Stereocenters

The development of
enantioselective carbon–carbon bond couplings
catalyzed by nonprecious metals is highly desirable in terms of cost
efficiency and sustainability. The first nickel-catalyzed enantioselective
Mizoroki–Heck coupling is reported. This transformation is
accomplished via mild reaction conditions, leveraging on QuinoxP*
as a chiral ligand to afford oxindoles containing quaternary stereocenters.
Good reactivity and selectivity are observed in the presence of various
functional groups. Computational studies suggest that the oxidative
addition assembles an atropisomeric intermediate responsible for the
facial selectivity of the insertion step.