Alkyne Carboamination with Imines Catalyzed by [pyTiClN(-tol)].

α,β-unsaturated imines are valuable functional groups that lack a general, reliable synthetic route. Here, we report that simple Ti imido halide precatalysts of the type [pyTiClN(Ar)] can catalyze alkyne carboamination with imines, yielding highly substituted α,β-unsaturated imines. [pyTiClN(Ar)] complexes can catalyze an expanded scope of substrates relative to earlier-reported cationic Ti complexes, albeit with modest yields. Several key side products of carboamination have been identified, indicating that low-valent Ti species resulting from catalyst decomposition may be limiting productive catalysis.