With an unusual electronic distribution isocyanides are versatile synthetic precursors in multi-component reactions and metal-catalyzed transformations. The strong σ-donation capability of the carbon atom of isocyanides to metals promotes the corresponding back donation of electrons from the metals to the π* orbital of the isocyanide unit. While such a complexation between isocyanides and metals can promote various coupling reactions, the carbon α to the isocyanide moiety can be also functionalized. Thus, the α-isocyano compounds readily participate in the stereo- and regioselective synthesis of various heterocycles. Previously, our group disclosed the catalytic asymmetric aldol reaction of α-isocyano esters in the presence of cooperative catalyst system of thiourea and chiral Co(I)-Brucine Diol complexes. In addition, we recently explored the click chemistry feature of α-isocyano compounds in the 1,2-bond migration strategy to functionalized pyrroles. With an aim of further extending the chemistry of α-isocyano compounds, we prepared yet unknown α-isocyano compounds and utilized them in the aldol as well as Mannich reactions. In this presentation, we will discuss the stereochemical rationale for the asymmetric aldol and Mannich reactions using α-isocyano compounds.