P450酶启发的染料后修饰铁卟啉MOF光催化氧化  

Cytochrome P450 enzyme-inspired photocatalytic C—H oxidation by organic dye post-synthetically modified Fe-porphyrin-based MOF

作　　者：张森 张铁欣 何成[1] 段春迎[1] ZHANG Sen;ZHANG Tiexin;HE Cheng;DUAN Chunying(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China)

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116024

出　　处：《精细化工》2020年第12期2527-2533,2553,共8页Fine Chemicals

基　　金：国家自然科学基金(21971031,21890381,U1608224)。

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(6.25μmol),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。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(6.25μmol),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.

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 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]