仿生四齿胺基吡啶锰催化剂/H2O2的醇类化合物高效氧化: 间歇和连续流研究

doi:10.6023/cjoc202508025

有机化学 ›› 2026, Vol. 46 ›› Issue (3): 986-992.DOI: 10.6023/cjoc202508025 上一篇下一篇

研究论文

仿生四齿胺基吡啶锰催化剂/H₂O₂的醇类化合物高效氧化: 间歇和连续流研究

夏春年^a^,^*(), 陈凯林^a, 金诺琪^a, 南欣卉^a, 汪兵洋^b^,^*(), 吴馨怡^a, 孙强盛^b, 孙伟^b^,^*()

^a 浙江工业大学药学院杭州 310014
^b 中国科学院兰州化学物理研究所低碳催化与二氧化碳利用国家重点实验室低碳催化与二氧化碳利用国家重点实验室兰州 730000

收稿日期:2025-08-28 修回日期:2025-11-01 发布日期:2025-12-09
通讯作者: 夏春年, 汪兵洋, 孙伟
基金资助:
国家自然科学基金(22361142751); 国家自然科学基金(22372183); 国家自然科学基金(22302213); 甘肃省重大科技专项(22ZD6GA003); 及中国科学院兰州化学物理研究所重点培育(ZYFZFX-9)

Efficient Oxidation of Alcohols Using a Bioinspired Tetradentate Aminopyridine Manganese Catalyst with H₂O₂: Batch and Continuous Flow Studies

Chunnian Xia^a^,^*(), Kailin Chen^a, Nuoqi Jin^a, Xinghui Nan^a, Bingyang Wang^b^,^*(), Xinyi Wu^a, Qiangsheng Sun^b, Wei Sun^b^,^*()

^a College of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014
^b State Key Laboratory for Low Carbon Catalysis and CO₂ Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000

Received:2025-08-28 Revised:2025-11-01 Published:2025-12-09
Contact: Chunnian Xia, Bingyang Wang, Wei Sun
Supported by:
National Natural Science Foundation of China(22361142751); National Natural Science Foundation of China(22372183); National Natural Science Foundation of China(22302213); Major Project of Gansu Province(22ZD6GA003); Major Program of the Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences(ZYFZFX-9)

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摘要/Abstract

仿生四齿胺基吡啶锰配合物(Mn-N4)已在各种选择性氧化反应中展示出优异的催化活性. 报道了一系列Mn-N4的合成及其在催化仲醇氧化中的应用. 该方法利用过氧化氢(H₂O₂)作为环境友好的氧化剂, 并加入少量乙酸作为添加剂. 值得注意的是, 该催化剂体系的连续流工艺实现了快速转化, 将反应时间从传统间歇体系的90 min缩短到连续流工艺中的停留时间1.6 min. 这种方法为仲醇的工业氧化提供了一种有前途且实用的策略, 显示出更广泛的应用潜力.

关键词: 仿生催化, 醇的氧化, 锰配合物, 连续流

Bioinspired manganese complexes with tetradentate aminopyridine ligands (Mn-N4) have shown excellent promise as effective catalysts for various selective oxidation reactions. The synthesis of a series of Mn-N4 and their application in the catalytic oxidation of secondary alcohols are reported. This method utilizes hydrogen peroxide as an environmentally benign oxidant with a small amount of acetic acid as an additive. Notably, the continuous-flow process using this catalyst system achieves rapid conversion, reducing the reaction time from 90 min in a traditional batch system to 1.6 min residence time in the continuous-flow process. This approach offers a promising and practical strategy for the industrial oxidation of secondary alcohols, demonstrating significant potential for broader applications.

Key words: bioinspired catalysis, oxidation of alcohol, manganese complex, continuous flow

引用此文

夏春年, 陈凯林, 金诺琪, 南欣卉, 汪兵洋, 吴馨怡, 孙强盛, 孙伟. 仿生四齿胺基吡啶锰催化剂/H₂O₂的醇类化合物高效氧化: 间歇和连续流研究[J]. 有机化学, 2026, 46(3): 986-992.

Chunnian Xia, Kailin Chen, Nuoqi Jin, Xinghui Nan, Bingyang Wang, Xinyi Wu, Qiangsheng Sun, Wei Sun. Efficient Oxidation of Alcohols Using a Bioinspired Tetradentate Aminopyridine Manganese Catalyst with H₂O₂: Batch and Continuous Flow Studies[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 986-992.

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图/表 5

Scheme 1. Carboxylic acid-assisted heterolytic O—O bond cleavage mechanism

Entry	Catalyst	AcOH	GC conv./%	GC yield/%
1	Mn-1	1	99	99
2	Mn-1	0.3	36	35
3	Mn-1	0.5	63	60
4	Mn-2	1	5	4
5	Mn-2	6	35	31
6	Mn-3	1	26	24
7	Mn-3	3	64	63
8	Mn-3	6	99	99

Table 1. Optimization of alcohol oxidation reaction conditiona

Table 2. Substrate scope for the oxidation of secondary alcoholsa

Scheme 2. Continuous flow process for alcohol oxidation with the Mn-1 (0.05 mol%)/H2O2 (1.5 equiv.)/AcOH (1 equiv.) (each reaction module is 8 mL)

Entry	Substrate concentration/(mol•L^－l)	Residence time/min	Yield/%
1	1	1.6	100
2	1	1.6	46
3^b	0.5	3.2	60

Table 3. Development of Mn-1 catalytic system for the oxidation of secondary alcohols in flow systema

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仿生四齿胺基吡啶锰催化剂/H₂O₂的醇类化合物高效氧化: 间歇和连续流研究

Efficient Oxidation of Alcohols Using a Bioinspired Tetradentate Aminopyridine Manganese Catalyst with H₂O₂: Batch and Continuous Flow Studies

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