一价铜掺杂TiO2催化含氮杂环的氧化脱氢

doi:10.6023/cjoc202601029

摘要/Abstract

在温和条件下, Cu(I)-TiO₂催化剂能够高效催化含氮杂环的氧化脱氢反应, 以分子氧为唯一氧化剂, 实现良好的转化率和选择性. 此外, 对该催化体系的可放大性及其在有价值分子合成中的应用进行了研究. 该催化剂表现出良好的稳定性与可重复使用性, 在前5次循环中活性和选择性基本保持不变, 循环至第10次时仍可实现90.0%的转化率和93.1%的选择性. 对照实验和X射线光电子能谱(XPS)分析表明, Cu^＋富集表面物种是关键活性位, 并提出了一个涉及界面电子转移与自由基中间体的可能反应机理.

关键词: 一价铜, 含氮杂环, 氧化脱氢, 非均相催化

Under mild conditions, the Cu(I)-TiO₂ catalyst efficiently catalyzes the oxidative dehydrogenation of N-hetero- cycles using molecular oxygen as the sole oxidant, affording good conversion and selectivity. In addition, the scalability of the catalytic system and its application in the synthesis of valuable molecules were investigated. The Cu(I)-TiO₂ catalyst shows good stability and reusability, maintaining nearly unchanged activity and selectivity during the first five cycles and still affording 90.0% conversion and 93.1% selectivity in the tenth run. Control experiments together with X-ray photoelectron spectroscopy (XPS) analysis suggest that Cu^＋-rich surface species are the key active sites, and a plausible mechanism involving interfacial electron transfer and radical intermediates is proposed.

Key words: Cu(I), N-heterocycles, oxidative dehydrogenation, heterogeneous catalysis

引用此文

黄丰盛, 陈鹏飞, 冯裕发, 顾龙勤, 周维友, 何明阳, 戴璇. 一价铜掺杂TiO₂催化含氮杂环的氧化脱氢[J]. 有机化学, 2026, 46(8): 3227-3236.

Fengsheng Huang, Pengfei Chen, Yufa Feng, Longqin Gu, Weiyou Zhou, Mingyang He, Xuan Dai. Cu(I)-Doped TiO₂ for Oxidative Dehydrogenation of N-Heterocycles[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3227-3236.

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图/表 11

Figure 1. XRD patterns of prepared catalysts

Figure 2. N2 adsorption/desorption isotherms of prepared catalysts

Figure 3. (a) XPS spectra of Cu(I)-TiO2 and Cu-TiO2 samples; (b) Cu LMM Auger electron spectrum of Cu(I)-TiO2

Entry	Solvent	T/℃	Reaction time/h	Yield/%
1^a	DMF	100	6	78
2^a	MeCN	100	6	<5
3^a	Mesitylene	100	6	84
4^a	1,4-Dioxane	100	6	32
5^a	PhCN	100	6	69
6^a	Trifluorotoluene	100	6	6
7^a	Mesitylene	80	6	55
8^a	Mesitylene	120	6	94
9^a	Mesitylene	130	6	95
10^a	Mesitylene	120	2	36
11^a	Mesitylene	120	4	66
12^a	Mesitylene	120	7	94
13^a	Mesitylene	120	8	94
14^b	Mesitylene	120	6	80
15^c	Mesitylene	120	6	94
16^d	Mesitylene	120	6	94

Table 1. Optimization of reaction conditions for the oxidative dehydrogenation of THQ

Scheme 1. Substrate scope for the oxidative dehydrogenation of THQ Reaction conditions: substrate (0.5 mmol), mesitylene (2.0 mL), Cu(I)-TiO2 (50 mg), 6~15 h, O2 atmosphere, 120 ℃.

Scheme 2. Substrate scope for the oxidative dehydrogenation of indoline Reaction conditions: substrate (0.5 mmol), mesitylene (2.0 mL), Cu(I)-TiO2 (50 mg), 6 h, O2 atmosphere, 120 ℃.

Scheme 3. General transformations and substrate scope for Cu(I)-TiO2-catalyzed aerobic oxidation a Reaction conditions: substrate (1 mmol), Cu(I)-TiO2 (50 mg), Al- (NO3)3 (0.075 mmol), cyclohexanone (2 mL), 100 ℃, O2 atmosphere. b Without Al(NO3)3.

Scheme 4. Synthetic applications

Entry	Catalyst	Additive	Conv./%	Sel./%
1^a	Cu(I)-TiO₂	—	>99	94
2^a	—	—	Trace	—
3^b	Cu(I)-TiO₂	—	24	95
4^a	Cu-TiO₂	—	55	53
5^a	TiO₂	—	20	33
6^a	Cu(I)-TiO₂	BHT^c	61	40

Table 2. Control experiments for the oxidative dehydrogenation of THQ

Scheme 5. Control experiments

Scheme 6. Plausible reaction mechanism for the oxidative dehydrogenation of THQ

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一价铜掺杂TiO₂催化含氮杂环的氧化脱氢

Cu(I)-Doped TiO₂ for Oxidative Dehydrogenation of N-Heterocycles

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