image: In this work, we present a chemoenzymatic cascade for selective synthesis of chiral N-arylated aspartic acids from biomass-derived furfural and waste nitrophenols by merging robust photo- and electrocatalysis with stereoselective biocatalysis. Briefly, concurrent photoelectrocatalytic oxidation of furfural into maleic acid/fumaric acid at the anode and electrocatalytic hydrogenation of nitrophenols into value-added aminophenols at the cathode proceeded simultaneously. The products formed at the two electrodes were converted into N-arylated (S)-aspartic acids by a bienzymatic cascade.
Credit: Chinese Journal of Catalysis
Furfural has been recognized as one of the top value-added biomass-derived platform chemicals by the U.S. Department of Energy. Currently, furfural is produced from agroindustrial waste such as corncob and oat hull via acid-catalyzed xylan depolymerization/dehydration on a large scale with approximately 50% yields. It was reported that the global market of furfural reached approximately USD 523 million (the volume exceeding 300 kilotons) in 2021, and it was expected to grow at a compound annual growth rate (CAGR) of 6.5% from 2022 to 2030. Furfural has a heteroaromatic ring and an aldehyde functional group, which endow the chemical with high chemical reactivity and plasticity. More importantly, it has green chemical properties such as carbon neutrality and renewability. Nitrophenols (NPs) are prevalent pollutants in industrial wastewater, exhibiting significant teratogenic and carcinogenic properties.
Chemical catalysis offers advantages such as excellent functional group tolerance, high reactivity, and a broad substrate range. In contrast, biocatalysis provides benefits including mild reaction conditions, environmental friendliness, high regioselectivity and enantioselectivity. Chemoenzymatic cascade reactions can provide a novel mode of synthesis, achieving complementary advantages. Thus, high value-added chiral chemicals can be easily produced from readily available starting materials via integrated chemoenzymatic catalysis.
To this end, a team of researchers from the School of Food Science and Engineering at South China University of Technology, including Professor Ning Li, developed a chemoenzymatic cascade strategy for sustainable production of chiral N-arylated aspartic acids from furfural and waste. The brief content is as follows: concurrent photoelectrocatalytic oxidation of furfural into maleic acid (MA) and fumaric acid (FA) was significantly enhanced by combining catalyst and reaction engineering strategies including identification of a powerful photocatalyst meso-tetra(4-carboxyphenyl)porphyrin, continuous flow technique, enhancing dissolved O2 and paired electrosynthesis. The overall space-time yield (STY) approached 2.8 g L-1 h-1 in a fed-batch process, with the product titer of 28.3 g L-1. Besides, photoelectrosynthesis of MA/FA was effectively fueled by sunlight, with the STY of up to 3.6 g L-1 h-1. Both MA selectivity and yield could be facilely improved to around 89% by reducing the buffer concentrations. Paired electrosynthesis strategy not only resulted in greatly improved MA production at the anode, but also enabled nitrophenols (NPs) upcycling into value-added aminophenols (APs) at the cathode. The products formed in the two electrode chambers were converted into N-arylated (S)-aspartic acids by a bienzymatic (maleate cis-trans isomerase (MaiA) and ethylenediamine-N,N'-disuccinic acid (EDDS) lyase ) cascade.
The proof-of-concept study for chemoenzymatic synthesis of high-value chiral non-natural aspartic acids from biomass and waste was demonstrated with no requirement of intermediate isolation, despite low yields. Anyway, this work presents a multicatalytic approach for integrating selective biomass valorization and waste upcycling towards sustainable manufacture. This work was published in Chinese Journal of Catalysis (https://doi.org/10.1016/S1872-2067(24)60146-4).
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About the Journal
Chinese Journal of Catalysis is co-sponsored by Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Chinese Chemical Society, and it is currently published by Elsevier group. This monthly journal publishes in English timely contributions of original and rigorously reviewed manuscripts covering all areas of catalysis. The journal publishes Reviews, Accounts, Communications, Articles, Highlights, Perspectives, and Viewpoints of highly scientific values that help understanding and defining of new concepts in both fundamental issues and practical applications of catalysis. Chinese Journal of Catalysis ranks among the top one journals in Applied Chemistry with a current SCI impact factor of 15.7. The Editors-in-Chief are Profs. Can Li and Tao Zhang.
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Journal
Chinese Journal of Catalysis
Article Title
A chemoenzymatic cascade for sustainable production of chiral N-arylated aspartic acids from furfural and waste
Article Publication Date
3-Dec-2024