One‐pot Twostep Chemobiocatalytic Synthesis of a Furan Amino Acid from 5‐Hydroxymethylfurfural

Abstract Recently, catalytic valorization of biomass‐derived furans has received growing interest. 5‐Aminomethyl‐2‐furancarboxylic acid (AMFC), a furan amino acid, holds great promise in the aeras of polymer and pharmaceutical, but its synthesis remains limited. In this work, we report a chemobiocatalytic route toward AMFC by combining laccase‐TEMPO system and recombinant Escherichia coli (named E. coli _TAF) harboring ω‐transaminase (TA), L‐alanine dehydrogenase (L‐AlaDH) and formate dehydrogenase (FDH), starting from 5‐hydroxymethylfurfural (HMF). In the cascade, HMF is oxidized into 5‐formyl‐2‐furancarboxylic acid (FFCA) by laccase‐TEMPO system, and then the resulting intermediate is converted into AMFC by E. coli _TAF via transamination with cheap ammonium formate instead of costly organic amine donors, theoretically generating H 2 O and CO 2 as by‐products. The tandem process was run in a one‐pot twostep manner, affording AMFC with approximately 81 % yield, together with 10 % 2,5‐furandicarboxylic acid (FDCA) as by‐product. In addition, the scale‐up production of AMFC was demonstrated, with 0.41 g/L h productivity and 8.6 g/L titer. This work may pave the way for green manufacturing of the furan‐containing amino acid.