Nickel-Catalyzed Asymmetric Intramolecular Reductive Heck Reaction of Unactivated Alkenes.

An asymmetric Ni-catalyzed intramolecular reductive Heck reaction of unactivated alkenes tethered to aryl bromides has been accomplished, providing a variety of benzene-fused cyclic compounds bearing a quaternary stereogenic center in good to excellent yields and high enantioselectivities. A mechanism has been proposed, which involves the enantiodetermining migratory insertion and the following protonation with water or alcoholic solvents as the proton source.