The search for efficient methodologies to form CÀC bonds continues to challenge chemists who face the construction of organic molecules of increasing complexity and functions. Multifaceted functional-group transformations and the creation and control of new asymmetric centers are key steps in the total synthesis of organic molecules, with special emphasis on catalytic activation.[1] Atom economy and high chemo-, regio-, and stereoselectivity are also essential requisites of new, efficient synthetic reactions.