Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes.

The inter- or intramolecular oxidative carboamination of alkynes catalyzed by [py2 TiCl2 NPh]2 is reported. These multicomponent reactions couple alkenes, alkynes and diazenes to form either α,β-unsaturated imines or α-(iminomethyl)cyclopropanes via a TiII /TiIV redox cycle. Each of these products is formed from a common azatitanacyclohexene intermediate that undergoes either β-H elimination or α,γ-coupling, wherein the selectivity is under substrate control.