Synthesis of α‑Aminonitriles\nvia Ammonium-Catalyzed\nReactions of Aminoacetonitrile

α-Aminonitriles are not only broadly useful building\nblocks\nbut also structural motifs in bioactive molecules. The Strecker reaction\nis one of the most widely used methods for α-aminonitrile synthesis.\nHowever, a severe drawback in Strecker reactions is the required use\nof a stoichiometric amount of toxic cyanation reagents. Thus, the\ndevelopment of a greener and widely applicable method for the synthesis\nof aminonitriles from readily available starting materials presents\nan important yet unmet challenge. We developed a general and new method\nfor the synthesis of aminonitriles from readily available aminoacetonitrile.\nThis method utilized off-the-shelf ammonium salts as catalysts, tolerated\nair and moisture, and avoided the use of cyanation reagents, which\nrendered it a greener alternative to the widely practiced Strecker\nreaction approach. We further illustrated that chiral ammonium-catalyzed\nasymmetric reactions of <i>N</i>-arylidene aminoacetonitriles\ncould provide chiral α-tertiary and α-quaternary aminonitriles\nand α-aminonitriles bearing two continuous stereocenters.