Ligand-Free Copper-Catalyzed Oxidative Rearrangement of Tetrahydro-β-carbolines

doi:10.6023/cjoc202602003

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (7): 2789-2795.DOI: 10.6023/cjoc202602003 Previous Articles Next Articles

ARTICLE

无配体铜催化四氢-β-咔啉的氧化重排反应

李凌岳^†, 张嘉沛^†, 张硕, 崔露元, 刘希功^*(), 刘磊

山东大学化学与化工学院济南 250100

收稿日期:2026-02-02 修回日期:2026-03-21 发布日期:2026-05-13
作者简介:
†共同第一作者
基金资助:
国家自然科学基金(22571185); 国家自然科学基金(22425108); 国家重点研发计划(2024YFA1509204); 国家重点研发计划(2024YFA1509202); 山东省泰山学者计划和山东省自然科学基金(ZR2025MS252)

Ligand-Free Copper-Catalyzed Oxidative Rearrangement of Tetrahydro-β-carbolines

Lingyue Li^†, Jiapei Zhang^†, Shuo Zhang, Luyuan Cui, Xigong Liu^*(), Lei Liu

School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100

Received:2026-02-02 Revised:2026-03-21 Published:2026-05-13
Contact: *E-mail: xigongliu@sdu.edu.cn
About author:
†(These authors contributed equally to this work).
Supported by:
National Natural Science Foundation of China(22571185); National Natural Science Foundation of China(22425108); National Basic Research Program of China(2024YFA1509204); National Basic Research Program of China(2024YFA1509202); Taishan Scholar Program at Shandong Province, the Natural Science Foundation of Shandong Province(ZR2025MS252)

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Abstract

The oxidative rearrangement of indoles has emerged as a prominent and highly efficient strategy for accessing spirooxindoles, a privileged scaffold prevalent among bioactive molecules and natural products. Herein, a ligand-free copper-catalyzed oxidative rearrangement of indoles is reported, and structurally diverse spirooxindoles were obtained in 90%~96% yields under mild reaction conditions. The reaction exhibits excellent functional group tolerance and a broad substrate scope, with the ligand-free conditions significantly enhancing its synthetic utility.

Key words: ligand-free, earth-abundant metal catalysis, copper-catalysis, spirooxindole, oxidative rearrangement

Cite this article

Lingyue Li, Jiapei Zhang, Shuo Zhang, Luyuan Cui, Xigong Liu, Lei Liu. Ligand-Free Copper-Catalyzed Oxidative Rearrangement of Tetrahydro-β-carbolines[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2789-2795.

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References 12

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Entry	Catalyst	Oxidant	Solvent	Yield^b/%
1	Cu(OTf)₂	O₂	CH₂Cl₂	<5
2	Cu(OTf)₂	H₂O₂	CH₂Cl₂	<5
3	Cu(OTf)₂	K₂S₂O₈	CH₂Cl₂	<5
4	Cu(OTf)₂	TBHP	CH₂Cl₂	84
5	—	TBHP	CH₂Cl₂	8
6	Cu(OAc)₂	TBHP	CH₂Cl₂	35
7	CuSO₄	TBHP	CH₂Cl₂	40
8	Cu(acac)₂	TBHP	CH₂Cl₂	36
9	CuBr₂	TBHP	CH₂Cl₂	61
10	CuCl₂	TBHP	CH₂Cl₂	55
11	CuOTf	TBHP	CH₂Cl₂	80
12	Cu(OTf)₂	TBHP	CH₃CN	20
13	Cu(OTf)₂	TBHP	EtOAc	<10
14	Cu(OTf)₂	TBHP	Acetone	15
15	Cu(OTf)₂	TBHP	THF	<10
16	Cu(OTf)₂	TBHP	DCE	72
17	Cu(OTf)₂	TBHP	CHCl₃	92
18^c	Cu(OTf)₂	TBHP	CHCl₃	92
19^d	Cu(OTf)₂	TBHP	CHCl₃	44
20^c^,^e	Cu(OTf)₂	TBHP	CHCl₃	92
21^c^,^f	Cu(OTf)₂	TBHP	CHCl₃	90

Entry	Catalyst	Oxidant	Solvent	Yield^b/%
1	Cu(OTf)₂	O₂	CH₂Cl₂	<5
2	Cu(OTf)₂	H₂O₂	CH₂Cl₂	<5
3	Cu(OTf)₂	K₂S₂O₈	CH₂Cl₂	<5
4	Cu(OTf)₂	TBHP	CH₂Cl₂	84
5	—	TBHP	CH₂Cl₂	8
6	Cu(OAc)₂	TBHP	CH₂Cl₂	35
7	CuSO₄	TBHP	CH₂Cl₂	40
8	Cu(acac)₂	TBHP	CH₂Cl₂	36
9	CuBr₂	TBHP	CH₂Cl₂	61
10	CuCl₂	TBHP	CH₂Cl₂	55
11	CuOTf	TBHP	CH₂Cl₂	80
12	Cu(OTf)₂	TBHP	CH₃CN	20
13	Cu(OTf)₂	TBHP	EtOAc	<10
14	Cu(OTf)₂	TBHP	Acetone	15
15	Cu(OTf)₂	TBHP	THF	<10
16	Cu(OTf)₂	TBHP	DCE	72
17	Cu(OTf)₂	TBHP	CHCl₃	92
18^c	Cu(OTf)₂	TBHP	CHCl₃	92
19^d	Cu(OTf)₂	TBHP	CHCl₃	44
20^c^,^e	Cu(OTf)₂	TBHP	CHCl₃	92
21^c^,^f	Cu(OTf)₂	TBHP	CHCl₃	90

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无配体铜催化四氢-β-咔啉的氧化重排反应

Ligand-Free Copper-Catalyzed Oxidative Rearrangement of Tetrahydro-β-carbolines

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