A chemoenzymatic cascade for sustainable production of chiral N-arylated aspartic acids from furfural and waste  

用于糠醛和废物高值化转化为手性N-芳基天冬氨酸的化学/酶级联反应

作　　者：Guang-Hui Lu Jian Yu Ning Li 路光辉;余健;李宁(华南理工大学食品科学与工程学院,广东广州510640)

机构地区：[1]School of Food Science and Engineering,South China University of Technology,Guangzhou 510640,Guangdong,China

出　　处：《Chinese Journal of Catalysis》2024年第12期102-111,共10页催化学报(英文)

基　　金：国家重点研发计划(2021YFC_(2)102700);国家自然科学基金(21971076).

摘　　要：Both biomass valorization and waste upcycling are important routes to sustain the circular bioeconomy.In this work,we present a chemoenzymatic cascade for selective synthesis of chiral N-arylated aspartic acids from biomass-derived furfural and waste nitrophenols(NPs)by merging robust photo-and electrocatalysis with stereoselective biocatalysis.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 O_(2) 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 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 cascade.This work presents a multicatalytic approach for integrating selective biomass valorization and waste upcycling towards sustainable manufacture.生物质转化和废物升级再造是发展可循环生物经济的重要措施.糠醛是一种重要的生物基平台化合物,由秸秆和玉米芯等农业废弃物中的半纤维素水解/脱水得到,具有碳中性和可再生等绿色化学属性.硝基酚(NPs)是工业废水中一类常见的污染物,具有强烈的致畸性和致癌性.化学/酶级联反应是在一个反应器中进行化学催化和酶催化的多步反应,且无需进行中间体的分离纯化.化学/酶级联反应结合了两者的优点,即前者强劲的反应活性、稳定性和广阔的底物谱以及后者较好的选择性,为合成化学注入了新的契机.本文报道了一个集成电催化、光催化和生物催化转化糠醛和废物NPs合成手性N-芳基天冬氨酸的化学/酶级联反应途径.利用催化剂工程和反应工程策略(包括发现强效光催化剂—5,10,15,20-四(4-羧基苯基)卟啉(TCPP)),采用连续流技术,提高溶氧和成对电合成解决光/电催化体系间的不兼容性,提高同步光/电催化氧化糠醛合成马来酸(MA)和富马酸(FA)效率.研究结果表明,在阴极室利用反应动力学上更有利的NPs还原反应替换动力学缓慢的析氢反应,可有效地促进阳极室的电催化氧化反应,即糠醛氧化为糠酸(FCA),5-羟基-2(5H)-呋喃酮(HFO)氧化为MA及富马酸半醛氧化为FA.选用TCPP作为光催化剂不仅可以降低电催化剂4-乙酰氨基-2,2,6,6-四甲基哌啶-N-氧自由基对光催化氧化的干扰,而且可以促进光催化氧化FCA合成HFO.与分批式光反应器相比,管式连续流光催化不仅能增强传质和改善光透性,提高光催化氧化效率,而且易于放大和调控.增强溶氧能有效促进光/电催化氧化糠醛合成MA和FA.在分批补料工艺中,MA/FA的总时空产率(STY)接近2.8 g L^(-1) h^(-1) ,产品滴度达28.3 g L^(-1) .此外,研究还发现可以直接利用太阳光驱动MA/FA的光电合成,其STY高达3.6 g L^(-1) h^(-1) .MA的选择性可以通过改变缓冲液浓度�

关 键 词：Asymmetric synthesis Biomass conversion Continuous flow photocatalysis Paired electrosynthesis Waste upcycling 

分 类 号：O62[理学—有机化学]