Synthesis of Bis(hydroxylmethylfurfuryl)amine Monomers from 5‐Hydroxymethylfurfural

Abstract We report the synthesis of bis(hydroxylmethylfurfuryl)amine (BHMFA) from 5‐hydroxymethylfurfural (5‐HMF) by reacting 5‐HMF with primary amines in the presence of homogeneous Ru II catalysts having sterically strained ligands. BHMFA is a group of furan‐based monomers that offer great potential to form functional biopolymers with tunable properties. A range of primary amines, such as aliphatic and benzyl amines, are readily converted with 5‐HMF to form the corresponding BHMFA in good yields. The reaction proceeds through reductive amination of 5‐HMF with primary amine to form secondary amine, followed by reductive amination of 5‐HMF with in situ generated secondary amine to produce BHMFA.