Synthesis of Primary Amines via Reductive Amination of Aldehydes and Ketones Over a Ni‐Doped MFM‐300(Cr) Catalyst

Abstract The development of earth‐abundant metal‐based catalysts is an important goal for the synthesis of fine chemicals. Here, an active nickel catalyst supported on a robust metal–organic framework, MFM‐300(Cr), is reported which shows an exceptional performance for reductive amination, a reaction that has long been dominated by noble metals. Ni/MFM‐300(Cr) promotes the synthesis of 38 primary amines via reductive amination of their parent carbonyl compounds, including biomass‐derived aldehydes and ketones, using NH 3 in the presence of H 2 operating under relatively mild conditions (5 bar and 160 °C). X‐ray absorption spectroscopy confirms the formation of mixtures of metallic Ni 0 and Ni n+ active sites, while in situ inelastic neutron scattering, coupled with modeling, reveals details of the mechanism of catalysis involving the formation of N‐benzyl‐1‐phenylmethanediamine (BPDI) as an intermediate species in the generation of benzylamine. Cooperativity between Ni sites and MFM‐300(Cr) creates an optimal microenvironment for the efficient activation of carbonyl compounds and the selective production of primary amines using a non‐precious metal‐based catalyst.