The inverse first-order dependence in nbe indicates that following nbe dissociation from I, nbe does not then reassociate with nickel center prior to the rate-determining step. This absence of reassociation of alkene has also been observed by Hartwig and co-workers in their studies of anti-Markovnikov hydroarylation reactions. In contrast, previous studies by our group described a zero-order dependence in alkyne in the hydroarylation of alkynes, which was attributed to association of the alkyne to the nickel center prior to reductive elimination through a mechanism that otherwise patterns that described for nbe hydroarylation. In conclusion, a strategy for the intermolecular enantioselective hydroarylation of alkenes using a nickel-catalyzed ligand-to-ligand hydrogen transfer approach has been developed. The strategy involves an operationally simple approach using structurally well-defined NHC nickel(0) complexes that incorporate 1,5-hexadiene as ligand to improve reactivities. The method was applied to the enantioselective C-H functionalization under mild conditions with a wide heteroarene scope. This method was further examined with simple styrene derivatives, delivering 1,1-diaryl ethanes in good yields and modest enantioselectivities. The identification of a well-defined, sterically demanding C2-symmetric chiral NHC complex allows for intermolecular alkylation of a wider range of heteroarenes to occur without the need for Lewis acid additives.