Page 165 - 《精细化工》2020年第12期

第 37 卷第 12 期 精 细 化 工 Vol.37, No.12
2020 年 12 月 FINE CHEMICALS Dec. 2020

催化与分离提纯技术

P450 酶启发的染料后修饰铁卟啉

MOF 光催化氧化

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张 森，张铁欣 ，何 成，段春迎
（大连理工大学 精细化工国家重点实验室，辽宁 大连 116024）

摘要：受细胞色素 P450 酶氧化代谢的启发，将染料酸性红 87（Acid Red 87）后修饰到金属有机框架 PCN-222(Fe)
中，构筑了非均相拟酶光催化剂 Acid Red 87@PCN-222(Fe)，拉近了染料与铁卟啉中心的距离，利用光致电子转
移模拟 P450 的电子传递链。以 1-(4-甲氧基苯基)乙醇为模板底物，对光催化氧化的条件，如溶剂、电子牺牲剂、
氧源等进行筛选，得到优化反应条件为：高碘酸钠 53.5 mg（0.25 mmol），2,6-二甲基吡啶三氟甲磺酸盐 32.2 mg
（0.125 mmol），Acid Red 87@PCN-222(Fe) 12.0 mg（6.25 μmol），乙腈（2 mL），530 nm 波长 LED 光照反应 24 h。
催化剂重复使用 3 次后仍保持活性和晶态结构。该催化体系对苄基碳氢键氧化具有良好的底物适用范围，可应
用于非甾体类抗炎药匹美诺芬的区位选择性氧化，分离产率为 48%，该体系还可将芳基硫醚类化合物氧化成相
应的亚砜，体现其在精细化工制药、工业脱硫领域的应用潜质。
关键词：酶模拟；细胞色素 P450 酶；金属有机框架；有机染料；后修饰；光氧化；碳氢键活化；催化技术
中图分类号：O643.36; O644.1 文献标识码：A 文章编号：1003-5214 (2020) 12-2527-08

Cytochrome P450 enzyme-inspired photocatalytic C—H oxidation by

organic dye post-synthetically modified Fe-porphyrin-based MOF

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ZHANG Sen, ZHANG Tiexin , HE Cheng, DUAN Chunying
（State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China）

Abstract: Enzyme-inspired by oxidative metabolism of cytochrome P450, organic dye Acid Red 87 was
introduced into metal-organic framework (MOF) PCN-222(Fe) by post-synthetic modification to construct
heterogeneous enzyme-mimicking photocatalyst Acid Red 87@PCN-222(Fe), in which the proximal spatial
distance between the dye and Fe-porphyrin moiety was expected to facilitate the photoinduced electron
transfer for mimicking the electron transfer chain in P450. The reaction conditions of
1-(4-methoxyphenyl)ethan-1-ol as model substrate, such as solvent, electronic sacrificial agent, oxygen
source and so on were screened. The optimized conditions were obtained as follows: sodium periodate as
oxygen source 53.5 mg (0.25 mmol), 2,6-lutidine trifluoromethanesulfonate as proton source 32.2 mg
(0.125 mmol), Acid Red 87@PCN-222(Fe) as photocatalyst 12.0 mg (6.25 μmol), acetonitrile as solvent
2 mL, under 530 nm LED irradiation for 24 h. The MOF-based photocatalyst could be recycled and reused
for at least 3 times without remarkable deteriorations of catalytic reactivity and structural crystalline. This
photocatalytic benzylic C—H oxidation was of broad substrate scope under the optimal conditions, and the
®
highly regioselective benzylic oxidation of the nonsteroidal antiinflammatory drug, Pimeprofen could be
achieved in a isolated yield of 48%. This protocol could be further expended to the oxidation of aryl
thioethers into corresponding aryl sulfoxides, which demonstrated its application potential in the field of
pharmacy and industrial desulfurization.

收稿日期：2020-04-25; 定用日期：2020-05-16; DOI: 10.13550/j.jxhg.20200349
基金项目：国家自然科学基金（21971031，21890381，U1608224）
作者简介：张 森（1995—），男，硕士生，E-mail：731124466@qq.com。联系人：张铁欣（1983—），男，副教授，E-mail：
zhangtiexin@dlut.edu.cn。