Reaction discovery and investigations. Initially, we examined the model reaction of Nvinylindole 1a with an aryl bromide compound, representing a class of nucleophiles that has previously been used as monomers for polymeric materials and unexploited in asymmetric nickel-catalyzed reactions. Upon investigating a series of reaction parameters (Table and), we discovered that running of the cross-coupling partners at room temperature for 20 hours in the presence of NiI 2 •xH 2 O, a chiral bis-oxazoline ligand (L*1), a hydride source (diethoxy-methylsilane), and a base (KF) provides the desired product in 75% yield and 92% enantiomeric excess (ee) as a single isomer (entry 9). Inferior results were found with other chiral nitrogen-based ligands, such as pyridine-oxazoline (Pybox) and 2,2-bis(2oxazoline) (Bi-Ox) ligands (entries 1-4). Interestingly, the mixed solvent (DME/DCE) turned out as the best solvent to obtain both high yield and high enantioselectivity (entries 5-7), thus indicating the subtle interplay of reagents and solvents in this case. In addition, use of other nickel salts, NiCl 2 •DME and NiBr 2 •DME resulted in somewhat lower yields and ee's (entries 7-9). Reaction scope. The generality of this catalytic enantioselective method is broad (Table ).