Electrochemical Direct Acyloxylation of Indoles with Ammonium Carboxylates as Acyloxyl Sources

doi:10.6023/cjoc202604023

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3578-3586.DOI: 10.6023/cjoc202604023 Previous Articles Next Articles

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电化学条件下以羧酸铵为酰氧基源的吲哚直接酰氧基化反应

赫景瑞, 王蕴歆, 梅海波^*(), 韩建林^*()

南京林业大学化学工程学院江苏省林业资源高效加工利用协调创新中心南京 210037

收稿日期:2026-04-15 修回日期:2026-05-19 发布日期:2026-07-06
通讯作者: 梅海波, 韩建林
基金资助:
国家自然科学基金(21761132021)

Electrochemical Direct Acyloxylation of Indoles with Ammonium Carboxylates as Acyloxyl Sources

Jingrui He, Yunxin Wang, Haibo Mei^*(), Jianlin Han^*()

Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037

Received:2026-04-15 Revised:2026-05-19 Published:2026-07-06
Contact: Haibo Mei, Jianlin Han
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Natural Science Foundation of China(21761132021)

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Abstract

Electrochemical functionalization of indoles represents an efficient and green strategy for the synthesis of indole derivatives. Herein, we report for the first time an electrochemical C3 acyloxylation reaction of 2-arylindoles. This radical acyloxylation reaction uses tetrabutylammonium carboxylates as both the acyloxy sources and the electrolytes, affording acyloxylated indoles as products in moderate to excellent yields under catalyst- and oxidant-free conditions. Mechanistic studies disclose that this reaction proceeds via anodic oxidation of the indole to form a radical cation, followed by direct coupling with a carboxylate anion and subsequent deprotonation. The transformation features mild conditions, broad substrate scope, and scale-up applicability, which provides a new and green strategy for the synthesis of 3-acyloxyindoles.

Key words: 2-arylindoles, acyloxylation, electrochemical reaction, radical reaction, tetrabutylammonium acetate

Cite this article

Jingrui He, Yunxin Wang, Haibo Mei, Jianlin Han. Electrochemical Direct Acyloxylation of Indoles with Ammonium Carboxylates as Acyloxyl Sources[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3578-3586.

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Fig. & Tab. 8

References 17

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Entry	2/equiv.	Electrode	Solvent	Time/h	Temperature/℃	Current/mA	Yield^b/%
1	1.5	Pt/Pt	MeCN	5	60	5	22
2	1.5	Pt/Ni	MeCN	5	60	5	26
3	1.5	C/C	MeCN	5	60	5	26
4	1.5	C/Ni	MeCN	5	60	5	52
5	1.5	C/Pt	MeCN	5	60	5	65
6	1.5	C/SS	MeCN	5	60	5	55
7	1.5	C/Zn	MeCN	5	60	5	64
8	1.5	C/Pt	MeCN	5	60	5	37 ^c
9	1.2	C/Pt	MeCN	5	60	5	51
10	2	C/Pt	MeCN	5	60	5	58
11	3	C/Pt	MeCN	5	60	5	63
12	1.5	C/Pt	MeCN	5	80	5	55
13	1.5	C/Pt	MeCN	5	r.t.	5	54
14	1.5	C/Pt	1,4-dioxane	5	60	5	Trace
15	1.5	C/Pt	DMF	5	60	5	71
16	1.5	C/Pt	EtOH	5	60	5	Trace
17	1.5	C/Pt	DCE	5	60	5	Trace
18	1.5	C/Pt	DMSO	5	60	5	70
19	1.5	C/Pt	DMA	5	60	5	58
20	1.5	C/Pt	DMF	7	60	3	80
21	1.5	C/Pt	DMF	3	60	10	56

Entry	2/equiv.	Electrode	Solvent	Time/h	Temperature/℃	Current/mA	Yield^b/%
1	1.5	Pt/Pt	MeCN	5	60	5	22
2	1.5	Pt/Ni	MeCN	5	60	5	26
3	1.5	C/C	MeCN	5	60	5	26
4	1.5	C/Ni	MeCN	5	60	5	52
5	1.5	C/Pt	MeCN	5	60	5	65
6	1.5	C/SS	MeCN	5	60	5	55
7	1.5	C/Zn	MeCN	5	60	5	64
8	1.5	C/Pt	MeCN	5	60	5	37 ^c
9	1.2	C/Pt	MeCN	5	60	5	51
10	2	C/Pt	MeCN	5	60	5	58
11	3	C/Pt	MeCN	5	60	5	63
12	1.5	C/Pt	MeCN	5	80	5	55
13	1.5	C/Pt	MeCN	5	r.t.	5	54
14	1.5	C/Pt	1,4-dioxane	5	60	5	Trace
15	1.5	C/Pt	DMF	5	60	5	71
16	1.5	C/Pt	EtOH	5	60	5	Trace
17	1.5	C/Pt	DCE	5	60	5	Trace
18	1.5	C/Pt	DMSO	5	60	5	70
19	1.5	C/Pt	DMA	5	60	5	58
20	1.5	C/Pt	DMF	7	60	3	80
21	1.5	C/Pt	DMF	3	60	10	56

电化学条件下以羧酸铵为酰氧基源的吲哚直接酰氧基化反应

Electrochemical Direct Acyloxylation of Indoles with Ammonium Carboxylates as Acyloxyl Sources

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