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

doi:10.6023/cjoc202505013

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

Wen-Long Wang, Jia-Xu Wen, Fei Chen, Chunbo Bo, Min Li, Ning Liu, Zhi-Hong Du. 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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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