α-diimines are commonly used as supporting ligands for a variety of transition metals, especially in olefin polymerization catalysis. Their synthesis is usually performed through the acid-catalyzed condensation of anilines with α-diketones. Despite the simplicity of this approach, accessing unsymmetrical α-diimines through this method can be challenging. Herein, we report the intermolecular diamination of alkynes to afford α-diimines from [4+2]-cycloaddition/retrocycloaddition sequences of diazatitanacyclohexadienes with C-nitrosos. These diazatitanacycles can be accessed through the <i>in-situ</i> multicomponent coupling of Ti imidos with alkynes and nitriles, providing a 1-pot, 2-step oxidative alkyne diamination protocol to yield a range of unsymmetric diimines.

Titanium-mediated intermolecular diamination of alkynes via [4+2]-cycloaddition/retrocycloaddition of C-nitrosos with diazatitanacycles

ACS Spring Meeting 2021

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