The inter- or intramolecular oxidative carboamination of alkynes catalyzed by [py(2)TiCl(2)NPh](2) is reported. These multicomponent reactions couple alkenes, alkynes and diazenes to form either alpha,beta-unsaturated imines or alpha-(iminomethyl)cyclopropanes via a Ti-II/Ti-IV redox cycle. Each of these products is formed from a common azatitanacyclohexene intermediate that undergoes either beta-H elimination or alpha,gamma-coupling, wherein the selectivity is under substrate control.