Visible-Light-Mediated Ruthenium-Catalyzed para-Acylation and Difluoroalkylation of Aniline Derivatives

doi:10.6023/cjoc202604018

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (8): 3276-3287.DOI: 10.6023/cjoc202604018 Previous Articles Next Articles

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可见光介导钌催化苯胺衍生物对位酰基化和二氟烷基化

易千禧^†, 梁宸伟^†, 程瑶航, 安光辉^*()

黑龙江大学化学化工与材料学院哈尔滨 150080

收稿日期:2026-04-09 修回日期:2026-04-29 发布日期:2026-05-26
通讯作者: 安光辉
作者简介:
^†共同第一作者
基金资助:
黑龙江省普通本科高等学校青年创新人才培养计划(UNPYSCT-2017124)

Visible-Light-Mediated Ruthenium-Catalyzed para-Acylation and Difluoroalkylation of Aniline Derivatives

Qianxi Yi, Chenwei Liang, Yaohang Cheng, Guanghui An^*()

School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080

Received:2026-04-09 Revised:2026-04-29 Published:2026-05-26
Contact: Guanghui An
About author:
^†These authors contributed equally to this work.
Supported by:
University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2017124)

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Abstract

A visible light-mediated ruthenium-catalyzed method for the para-C—H acylation and difluoroalkylation of aniline derivatives is developed. This strategy avoids the high-temperature conditions required by traditional methods and exhibits good functional group tolerance. Mechanistic studies suggest that the ruthenium catalyst is first reduced to Ru(0), which then enters the catalytic cycle. The key pathway of acylation involves sequential defluorination and nucleophilic addition processes.

Key words: visible-light-mediated, ruthenium catalysis, para-acylation, para-difluoroalkylation

Cite this article

Qianxi Yi, Chenwei Liang, Yaohang Cheng, Guanghui An. Visible-Light-Mediated Ruthenium-Catalyzed para-Acylation and Difluoroalkylation of Aniline Derivatives[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3276-3287.

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Entry	Deviation from the standard conditions	Yield^b/%
1	None	60
2	Without light irradiation or [RuCl₂(p-cymene)]₂	0
3	Without Ar	0
4	RuCl₃ instead of [RuCl₂(p-cymene)]₂	13
5	[RuCl₂(benzene)]₂ instead of [RuCl₂(p-cymene)]₂	44
6^c	Ru₃(CO)₁₂ instead of [RuCl₂(p-cymene)]₂	57
7^c	2 h instead of 8 h	57
8	Cs₂CO₃, Na₂CO₃instead of K₂CO₃	18, 43
9	25 or 40 ℃ instead of 60 ℃	39, 43

Entry	Deviation from the standard conditions	Yield^b/%
1	None	60
2	Without light irradiation or [RuCl₂(p-cymene)]₂	0
3	Without Ar	0
4	RuCl₃ instead of [RuCl₂(p-cymene)]₂	13
5	[RuCl₂(benzene)]₂ instead of [RuCl₂(p-cymene)]₂	44
6^c	Ru₃(CO)₁₂ instead of [RuCl₂(p-cymene)]₂	57
7^c	2 h instead of 8 h	57
8	Cs₂CO₃, Na₂CO₃instead of K₂CO₃	18, 43
9	25 or 40 ℃ instead of 60 ℃	39, 43

Entry	Deviation from the standard conditions	Yield^b/% 4a
1	None	52
2^c	Standard condition in Table 1	28
3	Without light irradiation or [RuCl₂(p-cymene)]₂	0
4	Without Ar	0
5	RuCl₃ instead of [RuCl₂(p-cymene)]₂	20
6	[RuCl₂(benzene)]₂ instead of [RuCl₂(p-cymene)]₂	39
7	Ru₃(CO)₁₂ instead of [RuCl₂(p-cymene)]₂	52
8	30 min or 1 h instead of 2 h	52, 52
9	25 or 60 ℃ instead of 40 ℃	41, 27
10	Cs₂CO₃, Na₂CO₃instead of KHCO₃	42, 46

Entry	Deviation from the standard conditions	Yield^b/% 4a
1	None	52
2^c	Standard condition in Table 1	28
3	Without light irradiation or [RuCl₂(p-cymene)]₂	0
4	Without Ar	0
5	RuCl₃ instead of [RuCl₂(p-cymene)]₂	20
6	[RuCl₂(benzene)]₂ instead of [RuCl₂(p-cymene)]₂	39
7	Ru₃(CO)₁₂ instead of [RuCl₂(p-cymene)]₂	52
8	30 min or 1 h instead of 2 h	52, 52
9	25 or 60 ℃ instead of 40 ℃	41, 27
10	Cs₂CO₃, Na₂CO₃instead of KHCO₃	42, 46

可见光介导钌催化苯胺衍生物对位酰基化和二氟烷基化

Visible-Light-Mediated Ruthenium-Catalyzed para-Acylation and Difluoroalkylation of Aniline Derivatives

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