This Highlight Review sheds light on a neglected aspect of alkylnitriles in synthetic organic chemistry. The chemical inertness and highly polar nature of alkylnitriles have particular utility as a reaction solvent. Alkylnitriles, however, also serve as potential building blocks for constructing carbon frameworks of interest. Two decades of exploratory studies of this elusive reaction revealed competent catalytic systems that allow for catalytic and enantioselective coupling of alkylnitriles with electrophiles.