A hydrogen autotransfer reaction has been applied to the α-alkylation of ketones, with primary alcohols as the electrophilic component, either under homogeneous (using a Ru complex as catalyst) or under heterogeneous (using Ni nanoparticles) conditions. This process is both very efficient (concerning atom economy) and ecologically friendly (water as the only by-product generated). On the other hand, three multicomponent reactions, namely, the Strecker reaction (without any catalyst), the aza-Sakurai process (catalyzed by ferrite), and the addition of in situ generated Zn enolates to chiral sulfinylimines (catalyzed by Cu), have proven to be very efficient in the generation of a diversity of polyfunctionalized molecules.