聚合物氮化碳负载铜克级制备一种无需额外配体即可催化二级嘧啶-2-胺的碳-氮乌尔曼偶联反应的实用催化剂

doi:10.6023/cjoc202009014

摘要/Abstract

通过在550 ℃下煅烧硝酸铜与三聚氰胺前体, 可实现聚合物氮化碳负载铜(Cu/PCN)材料的克级制备. X射线光电子能谱(XPS)分析表明, 该材料中铜元素呈一价, 可在无需额外配体的条件下催化二级嘧啶-2-胺与芳卤代烃的碳-氮乌尔曼偶联反应, 以实现其氮官能团的修饰. 作为非均相催化剂, 该材料易于回收, 并可被重复使用至少五次而不失活. 该材料比传统的一价铜与钯催化剂更加活泼, 从而为制药工业合成含有嘧啶-2-胺结构的药物提供了一种高效而实用的催化剂.

关键词: 聚合物氮化碳, 铜, 催化, 碳-氮乌尔曼偶联反应, 嘧啶-2-胺

Cu/polymeric carbon nitride (PCN) can be prepared in 10 g scale by calcining Cu(NO₃)₂ with the melamine precursor at 550 ℃. X-ray photoelectron spectroscopy (XPS) analysis demonstrated that copper in the material was in Cu(I) form and it could catalyze the Ullmann-type C—N coupling reactions of pyrimidin-2-amine derivatives with aryl halides without additional ligand. As a heterogeneous catalyst, the material was recoverable and could be reused for at least five times without deactivation. This material was found to be even more active than traditional Cu(I) catalysts and Pd catalysts, affording an opportunity to develop the efficient and practical novel catalyst reagent for the synthesis of medicines containing pyrimidin-2-amine moieties in pharmaceutical industry.

Key words: polymeric carbon nitride (PCN), copper, catalysis, Ullmann-type C—N coupling reaction, pyrimidin-2-amine

引用此文

孙扬阳, 冯刚, 陈超, 刘永红, 张旭. 聚合物氮化碳负载铜克级制备一种无需额外配体即可催化二级嘧啶-2-胺的碳-氮乌尔曼偶联反应的实用催化剂[J]. 有机化学, 2021, 41(3): 1216-1223.

Yangyang Sun, Gang Feng, Chao Chen, Yonghong Liu, Xu Zhang. Gram-Scale Synthesis of Polymeric Carbon Nitride-Supported Copper: A Practical Catalyst for Ullmann-Type C—N Coupling Modifying Secondary Pyrimidin-2-amines without Additional Ligand[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1216-1223.

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Entry	Solvent	Base	T/℃	Yield^b/%
1	t-BuOH	t-BuOK	80	23
2	EtOH	t-BuOK	80^c	20
3	THF	t-BuOK	80^c	22
4	1,4-Dioxane	t-BuOK	80	28
5	Toluene	t-BuOK	80	16
6	1,4-Dioxane	KOH	80	20
7	1,4-Dioxane	NaOH	80	16
8	1,4-Dioxane	Pyridine	80	18
9	1,4-Dioxane	t-BuOK	90	45
10	1,4-Dioxane	t-BuOK	100	67
11	1,4-Dioxane	t-BuOK	110^c	82
12	1,4-Dioxane	t-BuOK	120^c	80
13^d	1,4-Dioxane	t-BuOK	110^c	44

Entry	Solvent	Base	T/℃	Yield^b/%
1	t-BuOH	t-BuOK	80	23
2	EtOH	t-BuOK	80^c	20
3	THF	t-BuOK	80^c	22
4	1,4-Dioxane	t-BuOK	80	28
5	Toluene	t-BuOK	80	16
6	1,4-Dioxane	KOH	80	20
7	1,4-Dioxane	NaOH	80	16
8	1,4-Dioxane	Pyridine	80	18
9	1,4-Dioxane	t-BuOK	90	45
10	1,4-Dioxane	t-BuOK	100	67
11	1,4-Dioxane	t-BuOK	110^c	82
12	1,4-Dioxane	t-BuOK	120^c	80
13^d	1,4-Dioxane	t-BuOK	110^c	44

Entry	Ar	X	R	3	Yield^b/%
1	Ph	I	Me	3a	82
2	4-FC₆H₄	I	Me	3b	60
3	4-ClC₆H₄	I	Me	3c	90
4	4-BrC₆H₄	I	Me	3d	72
5	4-MeC₆H₄	I	Me	3e	88
6	3,4-(Me)₂C₆H₃	I	Me	3f	65
7	4-MeOC₆H₄	I	Me	3g	80
8	3-MeOC₆H₄	I	Me	3h	80
9	2-MeOC₆H₄	I	Me	3i	75
10	4-PhC₆H₃	I	Me	3j	65
11	2-C₁₀H₇	I	Me	3k	98
12		I	Me	3l	92
13	4-(4-IC₆H₄)C₆H₄	I	Me	3m	60
14	4-MeOC₆H₄	I	PhCH₂^c	3n	53
15	Ph	Br	Me	3a	56, 60^d
16	4-ClC₆H₄	Br	Me	3c	68^d
17	4-MeC₆H₄	Br	Me	3e	52^d
18	Ph	Cl	Me	3a	26, 30^d

Entry	Ar	X	R	3	Yield^b/%
1	Ph	I	Me	3a	82
2	4-FC₆H₄	I	Me	3b	60
3	4-ClC₆H₄	I	Me	3c	90
4	4-BrC₆H₄	I	Me	3d	72
5	4-MeC₆H₄	I	Me	3e	88
6	3,4-(Me)₂C₆H₃	I	Me	3f	65
7	4-MeOC₆H₄	I	Me	3g	80
8	3-MeOC₆H₄	I	Me	3h	80
9	2-MeOC₆H₄	I	Me	3i	75
10	4-PhC₆H₃	I	Me	3j	65
11	2-C₁₀H₇	I	Me	3k	98
12		I	Me	3l	92
13	4-(4-IC₆H₄)C₆H₄	I	Me	3m	60
14	4-MeOC₆H₄	I	PhCH₂^c	3n	53
15	Ph	Br	Me	3a	56, 60^d
16	4-ClC₆H₄	Br	Me	3c	68^d
17	4-MeC₆H₄	Br	Me	3e	52^d
18	Ph	Cl	Me	3a	26, 30^d