Efficient Approach to Synthesizing 2,5-Bis(aminomethyl)furan from 5-Chloromethylfurfural via the Gabriel Synthesis through Trans-imination and Hydrogenation

Primary diamines are crucial building blocks for sustainable polymers, but their synthesis remains challenging due to their high susceptibility to polymerization. However, conventional BAF production from HMF via reductive amination is limited by polymerization side reactions, posing significant challenges for scaling up BAF production. Herein, this study presents a new strategy to suppress polymerization by using the Gabriel synthesis and a more nucleophilic alkylamine while modulating the trans-imination and hydrogenation activity with a Ni–Co@SiO2 catalyst. Kinetic analysis revealed the high selectivity of this strategy. In addition, the analysis of the mechanism indicated that the abundant active sites and activated hydrogen species in Ni–Co@SiO2 were crucial to the efficient production of highly concentrated BAF, achieving an impressive yield of 91.6% under mild conditions. This work presents a pioneering method for the preparation of BAF, which is essential for advancing the synthesis of primary diamines.