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

doi:10.6023/cjoc202601029

Abstract

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

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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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Fig. & Tab. 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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一价铜掺杂TiO2催化含氮杂环的氧化脱氢