Metalloenzyme-like catalytic systems oxidize amines to imines under environmentally friendly conditions.

Acting together: Low catalytic amounts of CuI and topaquinone‐like catalyst 1ox (see scheme) are sufficient to activate the α‐CH bond of primary amines, which are converted into alkylated imines under ambient conditions. This atom‐economical process tolerates the presence of various reactive functional groups and allows selective cross‐coupling of two amines.