The catalytic functionalization of α C-H bond of amines has become a powerful strategy for the synthesis of nitrogen-containing compounds. This presentation will discuss the first example of catalytic alkyne hydroaminoalkylation, where the α C-H bond of an amine is added across an unsaturated π bond of alkynes. Mechanistic insights of this reaction will be discussed based on the isolation and reactivity assessment of catalytically relevant intermediates. In addition, a cross-dehydrogenative coupling of pyridines with the α C-H bond of amines will be presented. In these reactions, the expanded coordination number at zirconium plays a critical role in enabling challenging reaction steps as supported experimentally and by DFT calculations.