α-Diimine Synthesis via Titanium-Mediated Multicomponent Diimination of Alkynes with C-Nitrosos

α-Diimines are commonly used as supporting ligands for a variety of transition metal-catalyzed processes, most notably in α-olefin polymerization. They are also precursors to valuable synthetic targets, such as chiral 1,2-diamines. Their synthesis is usually performed through acid-catalyzed condensation of amines with α-diketones. Despite the simplicity of this approach, accessing unsymmetrical α-diimines is challenging. Herein, we report the Ti-mediated intermolecular diimination of alkynes to afford a variety of symmetrical and unsymmetrical α-diimines through the reaction of diazatitanacyclohexadiene intermediates with C-nitrosos. These diazatitanacycles can be readily accessed in situ via the multicomponent coupling of Ti≡NR imidos with alkynes and nitriles. The formation of α-diimines is achieved through formal [4+2]-cycloaddition of the C-nitroso to the Ti and γ- carbon of the diazatitanacyclohexadiene followed by two subsequent cycloreversion steps to eliminate nitrile and afford the α- diimine and a Ti oxo.