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Recent catalytic advances on the sustainable production of primary furanic amines from the one‐pot reductive amination of 5‐hydroxymethylfurfural

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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 a plenty of 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 (H2) 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 industry. 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 and chemo-selective yielding 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.

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