Heterogeneous Copper Catalyzed Aerobic Oxidative Cross-Coupling of Tertiary Amines with Alkynes

doi:10.6023/cjoc202504020

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 156-166.DOI: 10.6023/cjoc202504020 Previous Articles Next Articles

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非均相铜催化的叔胺与炔烃需氧氧化交叉偶联反应

谭紫云^a^,^b, 杨新^b, 龚绍峰^b, 杨慧翎^b, 谢永燕^b, 张静雅^b, 冯浙泰^a, 李文艺^a^,^*(), 肖新生^b^,^*()

^a 衡阳师范学院化学与材料科学学院湖南衡阳 421000
^b 湖南科技学院化学与生物工程学院湖南永州 425199

收稿日期:2025-07-22 修回日期:2025-08-24 发布日期:2025-09-17
基金资助:
国家自然科学基金(22002037); 湖南省功能金属有机化合物重点实验室(2023HSKFJJ005); 及湖南省研究生科研创新(LXBZZ2024370)

Heterogeneous Copper Catalyzed Aerobic Oxidative Cross-Coupling of Tertiary Amines with Alkynes

Ziyun Tan^a^,^b, Xin Yang^b, Shaofeng Gong^b, Huiling Yang^b, Yongyan Xie^b, Jingya Zhang^b, Zhetai Feng^a, Wenyi Li^a^,^*(), Xinsheng Xiao^b^,^*()

^a College of Chemistry and Materials Science, Hengyang Normal University, Hengyang, Huanan 421000
^b College of Chemical and Biological Engineering, Hunan University of Science and Engineering, Yongzhou, Huanan 425199

Received:2025-07-22 Revised:2025-08-24 Published:2025-09-17
Contact: * E-mails: wyli2018@hynu.edu.cn; shengguoxiao@163.com
Supported by:
National Natural Science Foundation of China(22002037); Foundation of Key Laboratory of Functional Metal-Organic Com- pounds of Hunan Province(2023HSKFJJ005); Project of Hunan Province Graduate Student Scientific Research Innovation(LXBZZ2024370)

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Abstract

The synthesis method of propargylamines has always been the focus of research in organic synthetic methodology. A method of alkynylation of tertiary aliphatic amines with alkynes in the presence of copper doped zeolite Y as a catalyst and oxygen in the air as an oxidant has been developed. The most important feature of this reaction is that copper molecular siolite is used as catalyst, which avoids the intermolecular self-coupling of alkynes, and thus realizes the high efficiency propargylization of alkyl tertiary amines.

Key words: propargylamine, copper doped zeolite-Y, heterogeneous catalyst, cross-coupling reaction

Cite this article

Ziyun Tan, Xin Yang, Shaofeng Gong, Huiling Yang, Yongyan Xie, Jingya Zhang, Zhetai Feng, Wenyi Li, Xinsheng Xiao. Heterogeneous Copper Catalyzed Aerobic Oxidative Cross-Coupling of Tertiary Amines with Alkynes[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 156-166.

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Fig. & Tab. 9

Scheme 1. Synthetic method of propargylamine compounds

Figure 1. SEM images of six catalysts (a) CuCl, (b) Copper doped Zeolite Y1, (c) Copper doped Zeolite Y2, (d) Copper doped Zeolite Y3, (e) Copper doped Zeolite Y4, and (f) Copper doped Zeolite Y5

Figure 2. XRD patterns of copper doped zeolite-Y and a reference sample cuprous chloride

Figure 3. XPS patterns of copper doped zeolite-Y and a reference sample cuprous chloride

Entry	Catalyst/mol%	Solvent	Temp./℃	Yield^b/%
1	—	Toluene	100	0
2	Cu(OAc)₂	Toluene	100	12
3	CuI	Toluene	100	17
4	CuBr	Toluene	100	16
5	CuCl	Toluene	100	19
6	Y1	Toluene	100	48
7	Y2	Toluene	100	33
8	Y3	Toluene	100	52
9	Y4	Toluene	100	0
10	Y5	Toluene	100	48
11	Y3	MeOH	100	23
12	Y3	CHCl₃	100	39
13	Y3	DMSO	100	16
14	Y3	1,4-Dioxane	100	52
15	Y3	DCE	100	72
16	Y3	DCE	90	75
17	Y3	DCE	80	83
18	Y3	DCE	70	45
19	Y3	DCE	60	23
20^c	Y3	DCE	80	81

Table 1. Optimization of reaction paramentsa

Table 2. Substrate scope for alkynea,b

Table 3. Substrate scope for the tertiary aminesa,b

Scheme 2. Control experiments

Scheme 3. Possible mechanism for Cu(I)-catalyzed aerobic oxidative cross-coupling of tertiary amines with alkynes

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非均相铜催化的叔胺与炔烃需氧氧化交叉偶联反应

Heterogeneous Copper Catalyzed Aerobic Oxidative Cross-Coupling of Tertiary Amines with Alkynes

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Fig. & Tab. 9

References 30

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