The enantioselective organocatalytic methodologies described in this chapter are a clear demonstration of the enormous potentiality of metal‐free catalytic reductions. Despite the historical need for ...and continued interest in chiral amines, their synthesis remains challenging. In one case, binaphthol‐derived phosphoric acids have been successfully employed in a process that involves the use of a dihydropyridine‐based compound as the reducing agent. In another strategy the reducing agent is trichlorosilane; finally in the very last few years a novel approach has been developed to realize metal‐free hydrogenation of imines: The Frustrated Lewis Pair (FLP) method involves the use of a combination of a strong Lewis acid with a variety of sterically encumbered Lewis bases to activate hydrogen at ambient conditions. It is recognized that these chemical adducts could find application in catalytic hydrogenation reactions.
