Nature Catalysis, Published online: 24 August 2026; doi:10.1038/s41929-026-01598-5 C–N bond functionalization of aliphatic primary amines is severely hampered by the poor nucleofugality of the NH2 group. Now, a direct catalytic deaminative cyanation of aliphatic primary amines has been established to enable efficient nitrile synthesis, including an asymmetric variant.