A general strategy for the assembly of previously unknown tris(beta,beta,gamma-oximinoalkyl)amines from aliphatic nitro compounds and methyl vinyl ketone is described. The strategy involves N,N-bis(siloxy)enamines as key intermediates. The latter are accessible by double silylation of alkylnitro compounds. Nickel(II) and copper(II) complexes of tris(beta,beta,gamma-oximinoalkyl)amines are prepared and structurally characterized.