可见光介导钌催化苯胺衍生物对位酰基化和二氟烷基化

doi:10.6023/cjoc202604018

摘要/Abstract

开发了一种可见光介导的钌催化苯胺衍生物对位C—H酰基化及二氟烷基化方法. 该策略避免了传统方法中的高温条件且具有良好的官能团耐受性. 机理研究表明, 钌催化剂首先被还原为零价钌, 从而进行催化循环. 酰基化的关键路径涉及二氟甲基化中间体的顺序脱氟与亲核加成过程.

关键词: 可见光介导, 钌催化, 对位酰基化, 对位二氟烷基化

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

引用此文

易千禧, 梁宸伟, 程瑶航, 安光辉. 可见光介导钌催化苯胺衍生物对位酰基化和二氟烷基化[J]. 有机化学, 2026, 46(8): 3276-3287.

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