铜催化2-芳基吲哚酰基化/环化反应合成吲哚[2,1-α]异喹啉酮衍生物

doi:10.6023/cjoc202405027

有机化学 ›› 2025, Vol. 45 ›› Issue (1): 307-318.DOI: 10.6023/cjoc202405027 上一篇下一篇

研究论文

铜催化2-芳基吲哚酰基化/环化反应合成吲哚[2,1-α]异喹啉酮衍生物

杨梦娜, 唐裕才^*(), 蒋洁, 李佳丽, 潘若涵, 陈宇, 段京林, 张松柏

湖南文理学院化学与材料工程学院水处理功能材料湖南省重点实验室电镀废水回用技术湖南省工术研究中心湖南常德 415000

收稿日期:2024-05-21 修回日期:2024-06-26 发布日期:2024-07-25
基金资助:
湖南省教育厅科学研究基金(23B0650); 湖南省教育厅科学研究基金(23A0503); 湖南省自然科学基金(2022JJ30419); 大学生创新创业训练计划(S202110549001S)

Copper(I)-Catalyzed Acylation/Cyclization of 2-Aryl-N-acryloyl Indole toward Indolo[2,1-α]isoquinoline Derivatives

Mengna Yang, Yucai Tang(), Jie Jiang, Jiali Li, Ruohan Pan, Yu Chen, Jinglin Duan, Songbai Zhang

Hunan Provincial Engineering Research Center of Electroplating Wastewater Reuse Technology, Hunan Provincial Key Laboratory of Water Treatment Functional Materials, College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde, Hunan 415000

Received:2024-05-21 Revised:2024-06-26 Published:2024-07-25
Contact: *E-mail: yctang1009@163.com
Supported by:
Scientific Research Foundation of Hunan Provincial Education Department(23B0650); Scientific Research Foundation of Hunan Provincial Education Department(23A0503); Natural Science Foundation of Hunan Province(2022JJ30419); Innovation and Entrepreneurship Training Program for College Students(S202110549001S)

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摘要/Abstract

吲哚[2,1-α]异喹啉酮衍生物是一类重要的生物活性分子, 表现出良好的抗菌活性. 发展了一种以CuI为催化剂, 以叔丁基过氧化氢为氧化剂, 以2-芳基吲哚和苯甲酰肼为原料, 实现不饱和双键的自由基酰基化/环化反应构建吲哚[2,1-α]异喹啉酮衍生物的方法. 该方法具有良好的官能团耐受性, 一系列酰基取代的吲哚[2,1-α]异喹啉酮类化合物以中等到良好的收率得到. 自由基捕捉实验表明, 该反应可能经历了自由基历程.

关键词: 吲哚[2,1-α]异喹啉酮, CuI, 2-芳基吲哚, 苯甲酰肼, 酰基化/环化

Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity. In the present study, an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1- α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant. The present protocol exhibits good functional group tolerance, and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields. Radical trapping experiments indicated that the reaction may involve a radical process.

Key words: indolo[2,1-α]isoquinolin-6(5H)-ones, CuI, 2-aryl-N-acryloyl indoles, benzohydrazide, acylation/cyclization

引用此文

杨梦娜, 唐裕才, 蒋洁, 李佳丽, 潘若涵, 陈宇, 段京林, 张松柏. 铜催化2-芳基吲哚酰基化/环化反应合成吲哚[2,1-α]异喹啉酮衍生物[J]. 有机化学, 2025, 45(1): 307-318.

Mengna Yang, Yucai Tang, Jie Jiang, Jiali Li, Ruohan Pan, Yu Chen, Jinglin Duan, Songbai Zhang. Copper(I)-Catalyzed Acylation/Cyclization of 2-Aryl-N-acryloyl Indole toward Indolo[2,1-α]isoquinoline Derivatives[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 307-318.

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Entry	Catalyst	Solvent	Oxidant	Yield^b/%
1	FeCl₂•4H₂O	DCE	TBHP	26
2	TBAI	DCE	TBHP	Trace
3	Cu(OAc)₂	DCE	TBHP	16
4	CuI	DCE	TBHP	29
5	FeCl₃•6H₂O	DCE	TBHP	22
6^c	CuI	DCE	TBHP	45
7^d	CuI	DCE	TBHP	47
8^e	CuI	DCE	TBHP	50
9^e	CuI	EA	TBHP	52
10^e	CuI	CH₃CN	TBHP	67
11^e	CuI	THF	TBHP	16
12^e	CuI	DMF	TBHP	18
13^e	CuI	1,4-Dioxane	TBHP	32
14^e	CuI	DMSO	TBHP	37
15^e	CuI	CH₃CN	K₂S₂O₈	12
16^e	CuI	CH₃CN	DTBP	52
17^e	CuI	CH₃CN	BPO	46
18^e	CuI	CH₃CN	TBPB	50
19^e,f	CuI	CH₃CN	TBHP	44

Entry	Catalyst	Solvent	Oxidant	Yield^b/%
1	FeCl₂•4H₂O	DCE	TBHP	26
2	TBAI	DCE	TBHP	Trace
3	Cu(OAc)₂	DCE	TBHP	16
4	CuI	DCE	TBHP	29
5	FeCl₃•6H₂O	DCE	TBHP	22
6^c	CuI	DCE	TBHP	45
7^d	CuI	DCE	TBHP	47
8^e	CuI	DCE	TBHP	50
9^e	CuI	EA	TBHP	52
10^e	CuI	CH₃CN	TBHP	67
11^e	CuI	THF	TBHP	16
12^e	CuI	DMF	TBHP	18
13^e	CuI	1,4-Dioxane	TBHP	32
14^e	CuI	DMSO	TBHP	37
15^e	CuI	CH₃CN	K₂S₂O₈	12
16^e	CuI	CH₃CN	DTBP	52
17^e	CuI	CH₃CN	BPO	46
18^e	CuI	CH₃CN	TBPB	50
19^e,f	CuI	CH₃CN	TBHP	44

铜催化2-芳基吲哚酰基化/环化反应合成吲哚[2,1-α]异喹啉酮衍生物

Copper(I)-Catalyzed Acylation/Cyclization of 2-Aryl-N-acryloyl Indole toward Indolo[2,1-α]isoquinoline Derivatives

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