Finally, we determined that enantioselective β-selective hydroalkylation could be realized (Figure ). With slight modifications to the solvent and reaction temperature based on the reaction conditions for migratory βselective hydroalkylation, the protected allylamine 3a and alkyl iodide 2a coupled well to deliver the enantioenriched β-branched amine 6aa with a 96% GC yield, an 89% isolated yield and a good regio-and enantioselectivity profile (9.2:1 r.r. and 94% e.e.). The mixed DMF/ t BuOH solvent exhibited a slight advantage over the single solvents, such as DMAc, DMF, or THF, with regard to both regio-and enantioselectivity (entries 2~4). MeOH was inferior because its use resulted in low alkene conversion (entry 5). A slightly increased reaction temperature at 21 °C rather than 10 °C improved the yield (entry 6). Comparative results on other bisoxazoline ligands are also listed (see Supplementary Table for more details). More benzyl substitutions on the linkage of bisoxazoline improved the yield and enantioselectivity (L* versus L6 versus L7). Aryl substitution on the oxazoline ring performed better than other substitutions, even structurally similar indan substituents (L* versus L8). Conditions: 1a (0.10 mmol, 1.0 equiv), 2a (0.20 mmol, 2.0 equiv), nickel catalyst (0.01 mmol, 10 mol%), L (0.015 mmol, 15 mol%), silane (0.30 mmol, 3.0 equiv), base (0.30 mmol, 3.0 equiv), solvent (0.60 mL, 0.167 M), 12 h. a Yield refers to the total yield for the mixture of all regioisomers. b r.r. refers to the regioisomeric ratio of the major product to the sum of all other isomers. For alkene migratory hydroalkylation and enantioselective hydroalkylation, α-, β-and linear-selective products were observed; other regioisomers could hardly be detected.