We systematically screened all reaction parameters and determined that a combination of NiBr2 (diglyme) and bisoxazoline ligand L with (EtO)3SiH and K3PO4 (H2O) in DMAc at 10 °C was critical for success, and an 86% GC yield and a 12:1 r.r. were obtained. More detailed information on the changes of each reaction parameter is summarized in Figure . Careful selection of the bisoxazoline ligand played an extremely vital role in the success of this reaction. The structurally related bipyridine (L1 and L2), bioxazoline (L3), and pyridine-oxazoline (L4) ligands were tested and gave moderate to good yields with poor regioselectivities (1:3.6~1.7:1 r.r.). A small amount of the target product was observed when we used a diamine ligand (L5). Many other nickel catalysts could be used, such as NiBr2 and NiI2 (entry 2), but Ni(acac)2 was invalid for this reaction (entry 3). Many other oxygenbearing silanes, such as DEMS, PMHS and (MeO)3SiH, could be used instead of (EtO)3SiH with slightly decreased coupling efficiency and comparable regioselectivity (entry 4). Ph2SiH2 delivered a gratifying 8.1:1 regioisomeric ratio with a low 22% total yield (entry 5), while the less electrophilic hydrosilane Et3SiH provided no cross-coupling product (entry 6). K3PO4 without crystal water also performed well (entry 7); Na2CO3 provided excellent regioselectivity, but the coupling yield was unsatisfactory (entry 8); lower yields and poor regioselectivities were obtained using a medium strength base such as KF or CsF (entry 9). Various solvents were compared to the optimal solvent DMAc. Amide solvent, DMF, afforded a high regioisomeric ratio with a slightly decreased 75% yield (entry 10). Polar aprotic CH3CN, ether THF, and hydrocarbon solvents such as toluene and DCE were inferior and exhibited significantly reduced regioselectivities (entry 11). Finally, this hydroalkylation reaction could not be performed without nickel catalysts (entry 12); a halved yield of 42% with a roughly equal 11:1 regioisomeric ratio was obtained in the absence of the bisoxazoline ligand L (entry 13).