Molybdenum-catalyzed asymmetric allylic alkylation reactions were carried out using the inexpensive, air-stable, and readily available Mo(CO)6 as precatalyst. In situ IR was used to determine the required activation time and temperature required to achieve the maximum concentration of the ‘‘active’’ catalyst from the molybdenum-precatalyst and chiral ligand. Results from comparison studies are consistent with the notion that the same active catalyst is generated regardless of molybdenum-precatalyst.