Synthesis of β-Amino-α-iminonitriles and α,β-Diiminonitriles Enabled by Lewis Acid-Catalyzed Double Isocyanide Insertion with Imines

Lewis acid-catalyzed double isocyanide insertion with imines was disclosed for the efficient construction of synthetically useful functionalized iminonitriles in a chemoselective manner. Zn(OTf)₂ catalyzed the synthesis of β-amino-α-iminonitriles from ketimines, while in the case of aldimines, <i>α,β</i>-diiminonitriles could be achieved either from the oxidation of the obtained β-amino-α-iminonitriles or through the In(OTf)₃-catalyzed one-pot oxidative isocyanide insertion. Furthermore, various transformations of the versatile product demonstrate the remarkable synthetic potential inherent in the given protocol.