With respect to migratory α-selective hydroalkylation, we found that the increased reaction temperature led to a reversed α-selectivity that allowed for the production of 4aa with both high regioselectivity and an excellent coupling yield (Figure ). A good GC yield of 97% and a 94% isolated yield with a superb regioselectivity profile (>20:1 r.r.) resulted under similar reaction conditions for the migratory β-selective hydroalkylation shown in Figure , and only the modification was the increase in reaction temperature to 100 °C. Therefore, judicious selection of reaction temperatures, one of the most easily changed variables in organic synthesis, led to protocols that provide the regiodivergent α-and β-C-H alkylation products starting from a single alkene substrate.