The reaction between enantiopure amino acid amides and metal-coordinated isocyanides such as cis-[Cl2M(CNR)2] (M = Pd, Pt) and [ClAu(CNR)] affords chiral acyclic diaminocarbene complexes in 64 to 91% yields with full retention of configuration at stereogenic centers. Structural analysis of the representative Pdii complexes revealed isostructural enantiomeric pairs with slightly distorted square-planar geometry, featuring labile Pd–Cl bonds trans to the ADC ligand. © 2026 Mendeleev Communications.