Direct Catalytic Asymmetric Addition of Acetonitrile to Aldimines.

Despite significant advances in catalytic asymmetric reactions with decent stereocontrol, those using acetonitrile as a pronucleophile are often disregarded due to their low reactivity and insufficient enantioselectivity. Herein we report the resurgence of this reaction in the chemical toolbox with high enantioselectivity (avg. > 95% ee). The combined use of a Ni(II) complex ligated with a chiral biscarbene and tBuOK engages acetonitrile in the catalytic generation of an α-cyanocarbanion and subsequent highly enantioselective addition to aldimines.