Catalytic Synthesis of N-(5-Methylfurfuryl)aniline from Bio-Derived Carbohydrates

The value-added chemicals derived from lignocellulosic resources are mainly oxygen-containing compounds while nitrogen-containing compounds are also important in the industry and ambitiously desired to be obtained from bio-based carbohydrates. Here we report an efficient two-step approach from fructose under mild conditions to obtain N-(5-methylfurfuryl)aniline, a necessary nitrogenous intermediate for some important epoxyisoindoles which have good combat-Alzheimer's and antitumor biological activities. First, 5-methylfurfural was prepared with HI and H3PO3 in a biphasic solution from fructose, then it was isolated and used for N-(5-methylfurfuryl)aniline synthesis through reductive amination catalyzed by a heterogeneous palladium catalyst. Besides, the substrate scope of the amines was examined, and most of them showed very good results. With this approach, renewable N-(5-methylfurfuryl)aniline was produced from fructose in an overall yield of 62%.