Recent Catalytic Advances on the Sustainable Production of Primary Furanic Amines from the One-Pot Reductive Amination of 5-Hydroxymethylfurfural

5-Hydroxymethylfurfural (5-HMF) represents a well-known class of lignocellulosic biomass-derived platform molecules. With the presence of many reactive functional groups in the structure, this versatile building block could be valorized into many value-added products. Among well-established catalytic transformations in biorefinery, the reductive amination is of particular interest to provide valuable N-containing compounds. Specifically, the reductive amination of 5-HMF with ammonia (NH3) and molecular hydrogen (H-2) offers a straightforward and sustainable access to primary furanic amines [i. e., 5-hydroxymethyl-2-furfuryl amine (HMFA) and 2,5-bis(aminomethyl)furan (BAMF)], which display far-reaching utilities in pharmaceutical, chemical, and polymer industries. In the presence of heterogeneous catalysts contanining monometals (Ni, Co, Ru, Pd, Pt, and Rh) or bimetals (Ni-Cu and Ni-Mn), this elegant pathway enables a high-yielding and chemoselective production of HMFA/BAMF compared to other synthetic routes. This Review aims to present an up-to-date highlight on the supported metal-catalyzed reductive amination of 5-HMF with elaborate studies on the role of metal, solid support, and reaction parameters. Besides, the recyclability/adaptability of catalysts as well as the reaction mechanism are also provided to give valuable insights into this potential 5-HMF valorization strategy.

Automated summary

5-Hydroxymethylfurfural (5-HMF) is an important platform molecule derived from lignocellulosic biomass, which can be valorized into valuable compounds through catalytic transformations. The reductive amination of 5-HMF with ammonia and hydrogen offers a sustainable and straightforward approach to primary furanic amines, which have wide applications in various industries. This review highlights the metal-catalyzed reductive amination of 5-HMF, focusing on the role of metal, solid support, and reaction parameters, as well as the recyclability of catalysts and the reaction mechanism.