Mild and Selective Reductive Amination of Biomass‐Derived Oxygenates Into Diamines Over Ni ₃ C Nanoparticle Catalysts

ABSTRACT The catalytic reductive amination of biomass‐derived oxygenates represents an environmentally benign approach for producing valuable diamine compounds. However, existing catalytic systems based on non‐precious metal catalysts require high H 2 pressures (>3 MPa). This study demonstrates that hydroxyapatite‐supported nickel carbide nanoparticles (Ni 3 C NPs/HAP) efficiently catalyze the reductive amination of glycolaldehyde (GA) with dimethylamine to afford N,N,N′,N′ ‐tetramethylethylenediamine (TMEDA) under mild conditions. Notably, efficient catalysis was achieved using Ni 3 C NPs/HAP even under an H 2 pressure of 1 MPa, outperforming conventional Ni catalysts. Moreover, the catalyst was easily separable and reusable for more than 10 consecutive runs without loss of activity, highlighting its excellent durability. Furthermore, various secondary amines were successfully transformed into their corresponding diamines (6 examples, ≤77% yields). This system also enabled efficient conversion of sugars into TMEDA via sequential C─C bond cleavage and reductive amination (6 examples, ≤63% yields). Overall, this Ni 3 C NP catalyst system provides a highly efficient strategy for the synthesis of important amine derivatives and contributes to the development of green and sustainable synthetic methodologies.