Three-Component Asymmetric Ni-Catalyzed 1,2-Dicarbofunctionalization of Unactivated Alkenes via Stereoselective Migratory Insertion

An asymmetric 1,2-dicarbofunctionalization of unactivated
alkenes
with aryl iodides and aryl/alkenylboronic esters under nickel/bioxazoline
catalysis is disclosed. A wide array of aryl and alkenyl nucleophiles
are tolerated, furnishing the products in good yield and with high
enantioselectivity. In addition to terminal alkenes, 1,2-disubstituted
internal alkenes participate in the reaction, establishing two contiguous
stereocenters with high diastereoselectivity and moderate enantioselectivity.
A combination of experimental and computational techniques shed light
on the mechanism of the catalytic transformation, pointing to a closed-shell
pathway with an enantiodetermining migratory insertion step, where
stereoinduction arises from synergistic interactions between the sterically
bulky achiral sulfonamide directing group and the hemilabile bidentate
ligand.