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

doi:10.6023/cjoc202508025

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 986-992.DOI: 10.6023/cjoc202508025 Previous Articles Next Articles

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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

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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Abstract

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

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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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Fig. & Tab. 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

References 25

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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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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