电化学苄位区域选择性氧化反应研究

doi:10.1016/S1872-2067(24)60139-7

催化学报 ›› 2024, Vol. 67: 54-60.DOI: 10.1016/S1872-2067(24)60139-7

电化学苄位区域选择性氧化反应研究

奚亦凡^a, 高睿行^a, 方萍^a, 韩亚平^b(), 马聪^a, 梅天胜^a()

^a中国科学院大学, 中国科学院上海有机化学研究所, 金属有机化学国家重点实验室, 上海 200032
^b河北工业大学化工学院, 天津 300130

收稿日期:2024-09-02 接受日期:2024-09-10 出版日期:2024-11-30 发布日期:2024-11-30
通讯作者: 韩亚平,梅天胜
基金资助:
国家重点研发计划(2021YFA1500100);中国科学院战略重点研究计划项目(XDB0610000);国家自然科学基金项目(21821002);国家自然科学基金项目(22361142834);国家自然科学基金项目(22425111);国家自然科学基金项目(22101294);上海市科学与技术研究基金(21ZR1476500);宁波自然科学基金项目(2023J035)

Site-selective benzylic C-H oxidation through mediated electrolysis

Yi-Fan Xi^a, Rui-Xing Gao^a, Ping Fang^a, Ya-Ping Han^b(), Cong Ma^a, Tian-Sheng Mei^a()

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China
^bSchool of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China

Received:2024-09-02 Accepted:2024-09-10 Online:2024-11-30 Published:2024-11-30
Contact: Ya-Ping Han, Tian-Sheng Mei
Supported by:
National Key R&D Program of China(2021YFA1500100);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000);National Natural Science Foundation of China(21821002);National Natural Science Foundation of China(22361142834);National Natural Science Foundation of China(22425111);National Natural Science Foundation of China(22101294);S&TCSM of Shanghai(21ZR1476500);Natural Science Foundation of Ningbo(2023J035)

摘要/Abstract

摘要：

苄位氧化反应在化工制造和医药生产中应用广泛. 通过有机电合成, 利用电子作为清洁的氧化剂, 可以避免当量化学试剂的加入, 提高反应的原子经济性. 然而, 传统的直接电解方法存在电极电位过高的问题. 为解决该问题, 氢原子转移(HAT)分子电催化剂N-羟基马来酰亚胺(NHPI)被引入反应体系, 通过间接电解的方式使反应在温和条件下进行. 然而, 当面对多个键能相近、电性相似的碳氢键时, 该催化剂存在区域选择性不佳的挑战.

为了解决该挑战, 本文设想将Maruoka课题组(Angew. Chem. Int. Ed., 2020, 59, 14261-14264)报道的大位阻N-羟基马来酰亚胺(NHMI)催化剂与有机电合成相结合, 以利用其位阻效应来调控反应的区域选择性. 首先, 合成了一系列NHPI与NHMI的类似物, 并在标准反应条件下对其催化性能进行考察. 使用最优催化剂考察了反应的时间曲线, 并确定了反应的理想时间. 在最优条件下, 对不同位阻和电性特征的底物进行了考察. 研究结果表明, 当底物的一侧位阻逐渐增大时, 反应的区域选择性显著提高. 然而, 当底物一侧存在富电子基团(如环丙基或取代的苯基)时, 反应的区域选择性会发生逆转. 这是因为即使该碳氢键的位阻较大, HAT反应仍然更倾向于发生在富电子的碳氢键上. 将大位阻的NHMI催化剂与NHPI的催化效果进行比较, 本研究发现NHMI催化剂在大多数情况下表现出更优的区域选择性, 并且不存在二次氧化的问题, 为该催化剂在电化学体系下的其他应用提供参考, 也为后续HAT分子电催化剂的设计和优化提供借鉴. 在机理研究方面, 通过循环伏安曲线(CV)测定了底物与催化剂的氧化电位, 此外, 通过时间曲线、背景反应以及恒电位电解法等方法证明了HAT过程的存在.

综上所述, 本研究将大位阻NHMI催化剂应用在电化学氧化反应中, 一定程度上解决了NHPI催化的电化学氧化反应中存在区域选择性差的问题. 但是目前反应中还存在许多不足. 首先, 催化剂结构复杂, 易于在反应中降解. 其次, 该催化剂的氧化电位较高, 对含有敏感官能团的底物并不适用. 未来的研究中应着眼于开发新一代HAT试剂, 力求降低催化剂用量, 提高反应的经济性.

关键词: 有机电化学, 氢原子转移, 选择性氧化, N-羟基马来酰亚胺, 自由基氧化

Abstract:

A novel strategy for site-selective benzylic C-H oxidation has been developed through mediated electrolysis. A bulky maleimide N-oxyl radical (MINO) generated by proton-coupled electrochemical oxidation of N-hydroxymaleimide (NHMI), serves as a hydrogen atom-transfer mediator. Good-to-excellent site selectivity was observed among different substrates, providing a practical approach for site-selective benzylic C-H oxidation. Additionally, the hydrogen-atom transfer mechanism for C-H electrochemical oxidation allows the oxidation to proceed at much lower anode potentials relative to direct electrolysis and with minimal reliance on the substrate's electronic properties.

Key words: Organic electrochemistry, Hydrogen atom transfer, Site-selective oxidation, N-Hydroxymaleimide, Radical oxidation

奚亦凡, 高睿行, 方萍, 韩亚平, 马聪, 梅天胜. 电化学苄位区域选择性氧化反应研究[J]. 催化学报, 2024, 67: 54-60.

Yi-Fan Xi, Rui-Xing Gao, Ping Fang, Ya-Ping Han, Cong Ma, Tian-Sheng Mei. Site-selective benzylic C-H oxidation through mediated electrolysis[J]. Chinese Journal of Catalysis, 2024, 67: 54-60.

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图/表 7

Scheme 1. Challenges and solutions in selective benzylic oxidation.

Scheme 2. Optimization of the reaction conditions for the site selective oxidation of the substrate. Reaction conditions: substrate 1 (0.2 mmol), catalyst (0.04 mmol, 20 mol%), lutidine (0.1 mmol, 0.5 equiv.), 2,6-lutidine tetrafluoroborate (0.8 mmol, 0.1 mol L-1), DCE (8 mL), C-felt as anode, Pt as cathode, O2 (1 atm.), 30 °C, 0.5 mA, 2.5 V, 30 h. b Yields are determined by 1H NMR using CH2Br2 as internal standard. c Site-selectivity is determined by GC-FID.

Scheme 3. Correlation between time, and combined yield and ratio under standard conditions. Reaction conditions: substrate 1 (0.2 mmol), Catalyst I (0.04 mmol, 20 mol%), lutidine (0.1 mmol, 0.5 equiv.), 2,6-lutidine tetrafluoroborate (0.8 mmol, 0.1 mol L-1), DCE (8 mL), C-felt as anode, Pt as cathode, O2 (1 atm.), 30 °C, 0.5 mA, 2.5 V. Yields are determined by 1H NMR using CH2Br2 as internal standard. site-selectivities are determined by GC-FID.

Table 1 Substrate scope. a

Scheme 4. Intermolecular site-selective benzylic C-H oxidation of 16 and 17. Reaction condition: substrates (0.2 mmol), catalyst (0.04 mmol, 20 mol%), lutidine (0.1 mmol, 0.5 equiv.), 2,6-lutidine tetrafluoroborate (0.8 mmol, 0.1 mol L-1), DCE (8 mL), C-felt as the anode, Pt as cathode, O2 (1 atm.), 30 °C, 0.5 mA, 2.5 V, 30 h. Yields are determined by 1H NMR using CH2Br2 as internal standard, yields in parenthesis are separated yields of major products. Site-selectivities are determined by GC-FID.

Scheme 5. CV data of catalyst I. Scanning conditions: CVs are scanned using glassy carbon as working electrode. (a) background: 0.1 mol L-1 LiClO4 in MeCN (grey); (b) 5 mmol L-1 NHPI, 10 mmol L-1 pyridine in (a) (red); (c) 5 mmol L-1 Catalyst I, 10 mmol L-1 pyridine in (a) (light blue); (d) 5 mmol L-1 Catalyst I, 10 mmol L-1 pyridine, 8 mmol L-1 substrate 1 in (a) (blue); (e) 5 mmol L-1 Catalyst I, 10 mmol L-1 pyridine, 16 mmol L-1 substrate 1 in (a) (deep blue).

Scheme 6. Proposed mechanism for selective oxidation.

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电化学苄位区域选择性氧化反应研究

Site-selective benzylic C-H oxidation through mediated electrolysis

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