Access to Tetrasubstituted Tri(indolyl)methanes through Copper-Catalyzed Addition/Substitution Sequence

doi:10.6023/cjoc202007055

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (2): 757-765.DOI: 10.6023/cjoc202007055 Previous Articles Next Articles

Article

铜催化加成/取代串联反应构建四取代的三吲哚甲烷

王文博¹, 韩华彬¹, 王乐乐¹, 王琪琳¹^,^*(), 卜站伟¹^,^*()

1 河南大学化学化工学院河南开封 475004

收稿日期:2020-07-23 修回日期:2020-08-21 发布日期:2020-09-22
通讯作者: 王琪琳, 卜站伟
作者简介:
* Corresponding authors. E-mail: wangqilin@henu.edu.cn; buzhanwei@henu.edu.cn
基金资助:
国家自然科学基金(U1504206); 中国博士后科学基金(2020M672200); 河南大学研究生教育创新与质量提升计划(SYL19060137); 河南大学研究生教育创新与质量提升计划(SYL19030204)

Access to Tetrasubstituted Tri(indolyl)methanes through Copper-Catalyzed Addition/Substitution Sequence

Wenbo Wang¹, Huabin Han¹, Lele Wang¹, Qilin Wang¹^,^*(), Zhanwei Bu¹^,^*()

1 College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004

Received:2020-07-23 Revised:2020-08-21 Published:2020-09-22
Contact: Qilin Wang, Zhanwei Bu
Supported by:
the National Natural Science Foundation of China(U1504206); the China Postdoctoral Science Foundation(2020M672200); the Graduate Education Innovation and Quality Improvement Program of Henan University(SYL19060137); the Graduate Education Innovation and Quality Improvement Program of Henan University(SYL19030204)

1. cjoc202007055.pdf(3201KB)

Abstract

An efficient one-pot synthesis of highly crowded tetrasubstituted tri(indolyl)methanes has been achieved through the addition/substitution sequence of 3-acetylindoles and indoles under mild conditions. The key to the success was improving the reactivity of 3-acetylindoles by rationally installing the N-protecting groups. The salient features including easily accessible and low-cost starting materials, board substrate scope, simple operation and structurally useful products make this approach particularly attractive.

Key words: indole, tri(indolyl)methane, cascade reaction

Cite this article

Wenbo Wang, Huabin Han, Lele Wang, Qilin Wang, Zhanwei Bu. Access to Tetrasubstituted Tri(indolyl)methanes through Copper-Catalyzed Addition/Substitution Sequence[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 757-765.

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Entry	Cat.	Solvent	Yield^b/%
1	FeCl₃?6H₂O	MeCN	46
2	Fe₂(SO₄)₃	MeCN	82
3	Fe(OTf)₃	MeCN	72
4	CuCl₂?2H₂O	MeCN	77
5	CuBr₂	MeCN	98
6	Cu(OTf)₂	MeCN	82
7	p-TSA	MeCN	95
8	TFA	MeCN	—
9	CuBr₂	CHCl₃	72
10	CuBr₂	THF	34
11	CuBr₂	MeOH	77
12^c	CuBr₂	MeCN	77^d
13^e	CuBr₂	MeCN	75^d

Entry	Cat.	Solvent	Yield^b/%
1	FeCl₃?6H₂O	MeCN	46
2	Fe₂(SO₄)₃	MeCN	82
3	Fe(OTf)₃	MeCN	72
4	CuCl₂?2H₂O	MeCN	77
5	CuBr₂	MeCN	98
6	Cu(OTf)₂	MeCN	82
7	p-TSA	MeCN	95
8	TFA	MeCN	—
9	CuBr₂	CHCl₃	72
10	CuBr₂	THF	34
11	CuBr₂	MeOH	77
12^c	CuBr₂	MeCN	77^d
13^e	CuBr₂	MeCN	75^d

Entry	R¹	1	R²	R³	2	3	Yield^b/%
1	Ts	1a	Bn	H	2a	3a	98
2	Ns	1b	Bn	H	2a	3b	41
3	Ac	1c	Bn	H	2a	3c	52
4	Bz	1d	Bn	H	2a	3d	64
5	Boc	1e	Bn	H	2a	3e	44
6	Cbz	1f	Bn	H	2a	3f	63
7	CO₂Et	1g	Bn	H	2a	3g	43
8	Ts	1a	Me	H	2b	3h	75
9	Ts	1a	Et	H	2c	3i	57
10	Ts	1a	n-Pr	H	2d	3j	79
11	Ts	1a	i-Pr	H	2e	3k	80
12	Ts	1a	n-Bu	H	2f	3l	88
13	Ts	1a	Allyl	H	2g	3m	68
14	Ts	1a	Bn	5-CH₃	2h	3n	70
15	Ts	1a	Bn	6-CH₃	2i	3o	64
16	Ts	1a	Bn	5-OBn	2j	3p	71
17	Ts	1a	Bn	5-Cl	2k	3q	34
18	Ts	1a	Bn	5-Br	2l	3r	69
19	Ts	1a	Bn	6-Br	2m	3s	74
20	Ts	1a	Bn	5-CO₂Me	2n	3t	53
21	Ts	1a	Bn	5-NO₂	2o	3u	32

Entry	R¹	1	R²	R³	2	3	Yield^b/%
1	Ts	1a	Bn	H	2a	3a	98
2	Ns	1b	Bn	H	2a	3b	41
3	Ac	1c	Bn	H	2a	3c	52
4	Bz	1d	Bn	H	2a	3d	64
5	Boc	1e	Bn	H	2a	3e	44
6	Cbz	1f	Bn	H	2a	3f	63
7	CO₂Et	1g	Bn	H	2a	3g	43
8	Ts	1a	Me	H	2b	3h	75
9	Ts	1a	Et	H	2c	3i	57
10	Ts	1a	n-Pr	H	2d	3j	79
11	Ts	1a	i-Pr	H	2e	3k	80
12	Ts	1a	n-Bu	H	2f	3l	88
13	Ts	1a	Allyl	H	2g	3m	68
14	Ts	1a	Bn	5-CH₃	2h	3n	70
15	Ts	1a	Bn	6-CH₃	2i	3o	64
16	Ts	1a	Bn	5-OBn	2j	3p	71
17	Ts	1a	Bn	5-Cl	2k	3q	34
18	Ts	1a	Bn	5-Br	2l	3r	69
19	Ts	1a	Bn	6-Br	2m	3s	74
20	Ts	1a	Bn	5-CO₂Me	2n	3t	53
21	Ts	1a	Bn	5-NO₂	2o	3u	32

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铜催化加成/取代串联反应构建四取代的三吲哚甲烷

Access to Tetrasubstituted Tri(indolyl)methanes through Copper-Catalyzed Addition/Substitution Sequence

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