酶-金属单原子复合催化剂在一锅法生物-化学反应的应用

doi:10.1016/S1872-2067(22)64179-2

催化学报 ›› 2023, Vol. 44: 139-145.DOI: 10.1016/S1872-2067(22)64179-2

酶-金属单原子复合催化剂在一锅法生物-化学反应的应用

黎晓阳^a, 曹宇飞^b, 熊佳容^b, 李隽^c, 肖海^c^,^*(), 李昕阳^d, 苟清强^d, 戈钧^b^,^e^,^f^,^*()

^a南昌大学食品学院, 食品科学与技术国家重点实验室, 江西南昌 330047
^b清华大学化工系, 工业生物催化教育部重点实验室, 北京 100084
^c清华大学化学系, 北京 100084
^d中石化(北京)化工研究院有限公司, 北京 122000
^e清华深圳国际研究生院生物医药与健康工程研究所, 广东深圳 518055
^f深圳湾实验室生物医药健康技术与工程研究所, 广东深圳 518107

收稿日期:2022-07-11 接受日期:2022-08-22 出版日期:2023-01-18 发布日期:2022-12-08
通讯作者: 肖海,戈钧
基金资助:
国家重点研发计划(2021YFC2102800);国家自然科学基金(21878174);国家自然科学基金(22168024);清华大学-中国石油化工集团有限公司绿色化工联合研究院;佛山-清华产学研合作协同创新专项资金

Enzyme-metal-single-atom hybrid catalysts for one-pot chemoenzymatic reactions

Xiaoyang Li^a, Yufei Cao^b, Jiarong Xiong^b, Jun Li^c, Hai Xiao^c^,^*(), Xinyang Li^d, Qingqiang Gou^d, Jun Ge^b^,^e^,^f^,^*()

^aState Key Laboratory of Food Science and Technology, School of Food Science and Technology, Nanchang University, Nanchang 330047, Jiangxi, China
^bKey Laboratory for Industrial Biocatalysis, Ministry of Education, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
^cDepartment of Chemistry, Tsinghua University, Beijing 100084, China
^dSINOPEC (Beijing) Research Institute of Chemical Industry Co., Ltd., Beijing 122000, China
^eInstitute of Biopharmaceutical and Health Engineering, Tsinghua Shenzhen International Graduate School, Shenzhen 518055, Guangdong, China
^fInstitute of Biomedical Health Technology and Engineering, Shenzhen Bay Laboratory, Shenzhen 518107, Guangdong, China

Received:2022-07-11 Accepted:2022-08-22 Online:2023-01-18 Published:2022-12-08
Contact: Hai Xiao, Jun Ge
Supported by:
National Key Research and Development Program of China(2021YFC2102800);National Natural Science Foundation of China(21878174);National Natural Science Foundation of China(22168024);Tsinghua University-China Petrochemical Corporation Joint Institute for Green Chemical Engineering;Tsinghua-Foshan Innovation Special Fund (TFISF)

摘要/Abstract

摘要：

酶催化与金属单原子催化结合, 理论上可开发众多新的绿色化学合成反应, 是催化科学的一个重要研究前沿方向. 酶-金属单原子复合催化剂兼具酶和金属单原子催化剂的高效、高立体选择性等优点. 目前已成功构建的单原子分散金属催化剂的载体一般为刚性的无机载体, 利用柔性蛋白分子作为载体制备单原子分散金属催化剂的技术瓶颈问题在于蛋白分子具有柔性、构象易变的特点, 并且氨基酸残基与金属原子之间的相互作用力较弱, 蛋白分子表面的氨基酸残基难以与金属单原子稳定结合. 针对这样一个关键技术瓶颈问题, 我们建立了酶-金属单原子复合催化剂的光化学合成方法.

本文研究酶-金属单原子复合催化剂在生物-化学一锅级联反应合成联苯类手性醇中的催化性能. 联苯类手性醇是手性药物的重要中间体, 通常通过多步化学法或生物-化学级联法制备. 相比于多步化学法, 利用生物-化学级联反应制备联苯类手性化合物具有反应条件温和、选择性高、环境友好等优点. 采用光化学法合成脂肪酶-钯单原子复合催化剂(Pd₁/CALB-Pluronic), 通过球差矫正扫描透射电镜和扩展X射线吸收精细结构表征复合催化剂的形貌. 首先研究了Pd₁/CALB-Pluronic复合催化剂中单原子分散Pd催化的C‒C偶联反应催化效率, 然后考察了它在生物-化学一锅级联反应中的催化性能; 发现该催化剂在C‒C偶联反应中具有比常用的Pd均相催化剂和Pd非均相催化剂更好的活性. 在碘苯和苯乙炔的Sonogashira反应中, Pd₁/CALB-Pluronic的TOF值大于均相催化剂Pd(PPh₃)₄, 是多相商业催化剂Pd/C的3.5倍. Pd₁/CALB-Pluronic重复使用10次后, 活性仍保留97%, 具有很好的稳定性. 通过DFT计算分析催化反应路径, 提出了Pd₁/CALB-Pluronic复合催化剂的2价Pd单原子在Sonogashira反应中可能存在Pd^II/Pd^IV催化机理.

本文开发了(R)-1-(4-联苯)乙醇的生物-化学一锅级联反应合成新路线: Pd₁/CALB-Pluronic复合催化剂在30 ^oC的水溶液中催化(±)-1-(4-溴苯基)乙酸乙酯和苯硼酸反应生成(R)-1-(4-联苯)乙醇. 在该过程中, CALB催化的立体选择性水解反应和Pd单原子催化的C-C偶联反应同时进行. 其中, CALB催化(±)-1-(4-溴苯基)乙酸乙酯中的R型异构体水解为(R)-1-(4-溴苯基)乙醇, Pd单原子催化(R)-1-(4-溴苯基)乙醇与苯硼酸进行Suzuki反应生成(R)-1-(4-联苯)乙醇. Pd₁/CALB-Pluronic复合催化剂在30 ^oC下催化生物-化学一锅级联反应合成(R)-1-(4-联苯)乙醇, 其催化效率是商业催化剂Pd/C和CALB-Pluronic催化剂组合的31.3倍.

关键词: 化学-酶催化反应, 酶-金属复合催化剂, 单原子催化剂, 协同催化, 手性醇

Abstract:

Combining enzymatic and single-metal-atom catalysis is a promising approach for green chemical synthesis. We herein report a one-pot chemoenzymatic cascade reaction to asymmetric synthesize (R)-1-(4-biphenyl) ethanol by using the highly active and selective enzyme-metal-single-atom hybrid as the catalyst. We demonstrate that the Pd single atoms anchored lipase (Pd₁/CALB-P) can efficiently drive one-pot cascade reactions in aqueous solution at 30 °C to achieve facile synthesis of chiral biaryl alcohols, which are important pharmaceutical intermediates that traditionally require complex synthesis procedures. The rate of (R)-1-(4-biphenyl) ethanol formation catalyzed by Pd₁/CALB-P is more than 30-fold higher than that of the combination of commercial palladium on carbon (Pd/C) and lipase-pluronic conjugate (CALB-P). The enzyme-metal-single-atom hybrid catalyst provides a promising strategy for effectively merging the enzymatic and single-atom catalysis.

Key words: Chemoenzymatic reaction, Enzyme-metal hybrid catalyst, Single atom catalyst, Cooperative catalysis, Chiral alcohols

黎晓阳, 曹宇飞, 熊佳容, 李隽, 肖海, 李昕阳, 苟清强, 戈钧. 酶-金属单原子复合催化剂在一锅法生物-化学反应的应用[J]. 催化学报, 2023, 44: 139-145.

Xiaoyang Li, Yufei Cao, Jiarong Xiong, Jun Li, Hai Xiao, Xinyang Li, Qingqiang Gou, Jun Ge. Enzyme-metal-single-atom hybrid catalysts for one-pot chemoenzymatic reactions[J]. Chinese Journal of Catalysis, 2023, 44: 139-145.

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图/表 5

Fig. 1. Characterizations of Pd1/CALB-P. (a) Magnified AC-STEM image of Pd1/CALB-P; (b) Comparison of Fourier transforms and fitting results for EXAFS of Pd1/CALB-P; AC-STEM image of Pd1/CALB-P (c) and the corresponding elemental mapping (d) for Pd, Ti and O. Pd1/CALB-P was adsorbed on TiO2 and then calcined in air at 250 °C for better contrast.

Fig. 2. Catalytic performance of Pd in C?C coupling reactions. (a) Conversion versus reaction time. (b) ln(At/A0) versus reaction time, At and A0 stand for the concentration of iodobenzene at the intervals and at the initial stage; (c) Comparison of TOF for the Pd1/CALB-P, PdCl2, Pd/C, Pd(PPh3)4 and PdNPs/CALB-P in the Sonogashira reactions using iodobenzene and phenylacetylene as the substrates. (d) Reaction scheme and the performance of Pd1/CALB-P in the Sonogashira coupling of phenylacetylene and aryl halides. Yields (bars) and selectivities (circles) of products in Sonogashira couplings by using aryl halides (entries 1-9) as the substrates. Green color: Pd1/CALB-P, orange color: PdCl2. Each data point and error bar represent the mean and standard deviation from at least three independent measurements.

Fig. 3. Calculated free energy profile of the Sonogashira reaction pathway catalyzed by the model catalyst for Pd1/CALB-P.

Scheme 1. Synthesis of (R)-1-(4-biphenyl)ethanol by one-pot chemoenzymatic reaction.

Table 1 Productivity and selectivity of Pd1/CALB-P for the synthesis of (R)-1-(4-biphenyl)ethanol.

Catalyst	Yield (%)	Selectivity (%)	ee (%)	Rate ^d
Pd₁/CALB-P ^a	48	96	99.7	25
Pd(PPh₃)₄+CALB-P ^a	3	95	98.5	1.7
PdNPs/CALB-P ^a	6	90	99.5	3.1
Pd/C+CALB-P ^a	1.2	92	99.9	0.8
PdNPs/CALB-P ^b	14	84	99.5	3.6
Pd/C+CALB-P ^c	8	69	98.4	1.2

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酶-金属单原子复合催化剂在一锅法生物-化学反应的应用

Enzyme-metal-single-atom hybrid catalysts for one-pot chemoenzymatic reactions

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