Copper-Catalyzed Asymmetric Oxidative Homocoupling Reaction of 3-Hydroxy-2-naphthoates: Design and Optimization of Amino Acid-Based Ligands

doi:10.6023/cjoc202505013

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 167-180.DOI: 10.6023/cjoc202505013 Previous Articles Next Articles

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铜催化的3-羟基-2-萘甲酸酯的不对称氧化偶联反应:氨基酸类配体的设计与优化

王文龙, 温家旭, 陈飞, 薄春博, 李敏, 刘宁^*(), 杜智宏^*()

石河子大学化学化工学院化工绿色过程省部共建国家重点实验室培育基地新疆石河子 832003

收稿日期:2025-05-10 修回日期:2025-07-07 发布日期:2025-09-16
通讯作者: 刘宁, 杜智宏
基金资助:
国家自然科学基金(22201186); 石河子大学高层次人才启动基金(2022ZK005); 及新疆维吾尔自治区天池英才计划资助项目

Copper-Catalyzed Asymmetric Oxidative Homocoupling Reaction of 3-Hydroxy-2-naphthoates: Design and Optimization of Amino Acid-Based Ligands

Wang Wen-Long, Wen Jia-Xu, Chen Fei, Bo Chunbo, Li Min, Liu Ning^*(), Du Zhi-Hong^*()

State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003

Received:2025-05-10 Revised:2025-07-07 Published:2025-09-16
Contact: Liu Ning, Du Zhi-Hong
Supported by:
National Natural Science Foundation of China(22201186); Start-Up Foundation for High-Level Professionals of Shihezi University(2022ZK005); Tianchi Talent Project of Xinjiang Uygur Autonomous Region

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Abstract

A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates. By optimizing the reaction conditions, it was found that when using L3 (5 mol%) as the ligand, CuCl (5 mol%) as the catalyst, dichloromethane as the solvent, 2,2,6,6-tetra- methylpiperidine 1-oxyl (TEMPO)/O₂ as the oxidant, and under the reaction condition of 40 ℃, this method exhibited good substrate tolerance. Under these conditions, a series of chiral 1,1'-bi-2-naphthol (BINOL) derivatives were synthesized with yields of 45%~90% and enantioselectivities ranging from 50∶50 to 97∶3.

Key words: chiral amide ligand, copper catalyst, oxidative coupling, 3-hydroxy-2-naphthoate, 1,1'-bi-2-naphthol (BINOL)

Cite this article

Wang Wen-Long, Wen Jia-Xu, Chen Fei, Bo Chunbo, Li Min, Liu Ning, Du Zhi-Hong. Copper-Catalyzed Asymmetric Oxidative Homocoupling Reaction of 3-Hydroxy-2-naphthoates: Design and Optimization of Amino Acid-Based Ligands[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 167-180.

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Fig. & Tab. 7

References 51

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Entry	Ligand	Additive	Yield^b/%	e.r.^c
1	L1	—	20	58∶42
2	L2	—	32	54∶46
3	L3	—	15	97∶3
4	L4	—	10	64∶36
5	L5	—	11	94∶6
6	L6	—	Trace	—
7	L7	—	23	51∶49
8	L8	—	20	51∶49
9	L9	—	25	78∶22
10	L10	—	9	95∶5
11	L11	—	42	54∶46
12	L12	—	41	52∶48
13	L13	—	40	53∶47
14	L14	—	37	57∶43
15	L15	—	36	52∶48
16	L3	TEMPO	18	96∶4
17	L3	O₂	20	96∶4
18	L3	TEMPO/O₂	28	97∶3
19	L3	m-CPBA	NR	—
20	L3	DDQ	NR	—
21	L3	t-BuOOH	NR	—
22	L3	Ag₂CO₃	NR	—
23	L3	4Å MS	16	96∶4
24	L3	MgSO₄	47	87∶13
25	L3	Na₂SO₄	14	91∶9

Entry	Ligand	Additive	Yield^b/%	e.r.^c
1	L1	—	20	58∶42
2	L2	—	32	54∶46
3	L3	—	15	97∶3
4	L4	—	10	64∶36
5	L5	—	11	94∶6
6	L6	—	Trace	—
7	L7	—	23	51∶49
8	L8	—	20	51∶49
9	L9	—	25	78∶22
10	L10	—	9	95∶5
11	L11	—	42	54∶46
12	L12	—	41	52∶48
13	L13	—	40	53∶47
14	L14	—	37	57∶43
15	L15	—	36	52∶48
16	L3	TEMPO	18	96∶4
17	L3	O₂	20	96∶4
18	L3	TEMPO/O₂	28	97∶3
19	L3	m-CPBA	NR	—
20	L3	DDQ	NR	—
21	L3	t-BuOOH	NR	—
22	L3	Ag₂CO₃	NR	—
23	L3	4Å MS	16	96∶4
24	L3	MgSO₄	47	87∶13
25	L3	Na₂SO₄	14	91∶9

Entry	[Cu]		Solvent	Yield^b/%	e.r.^c
1	CuBr		CH₂Cl₂	NR	—
2	CuI		CH₂Cl₂	Trace	—
3	Cu₂O		CH₂Cl₂	Trace	—
4	Cu(OAc)₂		CH₂Cl₂	Trace	—
5	CuSO₄		CH₂Cl₂	NR	—
6	CuCl₂		CH₂Cl₂	37	58∶42
7	CuBr₂		CH₂Cl₂	25	53∶47
8	Cu(OTf)₂		CH₂Cl₂	6	79∶21
9	CuOAc		CH₂Cl₂	6	68∶32
10	CuCl		CHCl₃	18	96∶4
11	CuCl		CCl₄	16	63∶37
12	CuCl		DCE	21	83∶17
13	CuCl		PhMe	Trace	—
14	CuCl		MeOH	90	56∶44
15	CuCl		i-PrOH	76	58∶42
16	CuCl		HFIP	74	66∶34
17	CuCl		Dioxane	65	92∶8
18	CuCl		THF	45	89∶11
19	CuCl	MeCN		NR	—
20	CuCl	DMSO		NR	—

Entry	[Cu]		Solvent	Yield^b/%	e.r.^c
1	CuBr		CH₂Cl₂	NR	—
2	CuI		CH₂Cl₂	Trace	—
3	Cu₂O		CH₂Cl₂	Trace	—
4	Cu(OAc)₂		CH₂Cl₂	Trace	—
5	CuSO₄		CH₂Cl₂	NR	—
6	CuCl₂		CH₂Cl₂	37	58∶42
7	CuBr₂		CH₂Cl₂	25	53∶47
8	Cu(OTf)₂		CH₂Cl₂	6	79∶21
9	CuOAc		CH₂Cl₂	6	68∶32
10	CuCl		CHCl₃	18	96∶4
11	CuCl		CCl₄	16	63∶37
12	CuCl		DCE	21	83∶17
13	CuCl		PhMe	Trace	—
14	CuCl		MeOH	90	56∶44
15	CuCl		i-PrOH	76	58∶42
16	CuCl		HFIP	74	66∶34
17	CuCl		Dioxane	65	92∶8
18	CuCl		THF	45	89∶11
19	CuCl	MeCN		NR	—
20	CuCl	DMSO		NR	—

Entry	CuCl/mol%	TEMPO/mol%	Yield^b/%	e.r.^c
1^d	2.5	5	35	96∶4
2	2.5	5	46	96∶4
3	5	5	60	97∶3
4	10	5	42	95∶5
5	5	10	58	89∶11
6^e	5	5	87	97∶3

铜催化的3-羟基-2-萘甲酸酯的不对称氧化偶联反应:氨基酸类配体的设计与优化

Copper-Catalyzed Asymmetric Oxidative Homocoupling Reaction of 3-Hydroxy-2-naphthoates: Design and Optimization of Amino Acid-Based Ligands

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