A plug-and-play chemobiocatalytic route for the one-pot controllable synthesis of biobased C4 chemicals from furfural

作者：Huang, Yi-Min; Lu, Guang-Hui; Zong, Min-Hua; Cui, Wen-Jing; Li, Ning^*

来源：Green Chemistry, 2021, 23(21): 8604-8610.

DOI：10.1039/d1gc03001a

• PROMISING PLATFORM
• GREEN CHEMISTRY
• FUMARIC-ACID
• MALEIC-ACID
• OXIDATION
• BIOMASS
• VALORIZATION
• BACTERIAL
• REDUCTASE
• CATALYST

Chemobiocatalytic selective transformation is an attractive yet challenging task, due to the incompatibility issues between different types of catalysts. In this work, one-pot, multi-step cascades integrating biocatalysis with organo-, base- and photocatalysis in a plug-and-play fashion were constructed for the controllable synthesis of eight C4 chemicals from furfural. Furfural was converted to 5-hydroxy-2(5H)-furanone (HFO) by sequential biocatalytic oxidation and photooxygenation in phosphate buffer, in >90% yields. Ring opening and concurrent isomerization of HFO to fumaric semialdehyde (FSA) were readily realized under mild conditions by a weakly basic resin (e.g., DVB resin). The versatile intermediate FSA could be oxidized to fumaric acid (FA) using a laccase-2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) system, which was further upgraded to amino acids including l-aspartic acid (l-Asp) and beta-alanine (beta-Ala) by whole-cell catalysis. Notably, amino acids were obtained from biobased furfural in a one-pot, four-step process with yields of up to 75%, without the isolation of any intermediates. Besides, the scale-up synthesis of l-Asp was demonstrated. This work demonstrates the great potential of the combination of chemo- and biocatalysis for selective furfural valorization.

• 单位
  江南大学