可见光氧化还原催化吲哚的还原去芳构化反应

doi:10.6023/cjoc202512044

摘要/Abstract

报道了一种条件温和、高效的吲哚还原去芳构化策略, 在光氧化还原催化体系下, 以N,N-二异丙基乙胺(DIPEA)为有机还原剂(氢源、电子给体). 该方法兼容2-位取代和非取代的吲哚底物, 以高产率(最高达99%)合成了一系列结构多样的官能化吲哚啉衍生物. 研究还表明, 该方法具有良好的官能团耐受性和广泛的底物普适性. 此外, 放大实验和合成应用研究进一步证实了该策略在实际合成中的潜力.

关键词: 光氧化还原, 吲哚, 去芳构化, 吲哚啉, 自由基

An efficient photoredox catalytic system for the radical reductive dearomatization of indoles is developed. Employing N,N-diisopropylethylamine (DIPEA) as an organic reductant, the reaction proceeds under mild conditions. Both substituted and unsubstituted indoles at the 2-position are well tolerated, affording a series of structurally diverse functiona- lized indoline derivatives in high yields (up to 99%). This method exhibits good functional group compatibility and broad substrate scope. Furthermore, scale-up experiments and synthetic transformations demonstrate the potential utility of this strategy in practical synthesis.

Key words: photoredox, indole, dearomatization, indoline, radical

引用此文

杨丹, 李天真, 白靖宜, 张洪浩, 石枫. 可见光氧化还原催化吲哚的还原去芳构化反应[J]. 有机化学, 2026, 46(4): 1699-1712.

Dan Yang, Tianzhen Li, Jingyi Bai, Honghao Zhang, Feng Shi. Visible-Light Photoredox-Catalyzed Reductive Dearomatization of Indoles[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1699-1712.

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图/表 10

图1. 含吲哚啉结构的代表性天然产物与生物活性分子

Figure 1. Representative natural products and bioactive substances containing indolines

图式1. 光促进吲哚去芳构化反应合成吲哚啉衍生物

Scheme 1. Photoinduced dearomatization of indoles for the synthesis of indoline derivatives

Entry	PC	Solvent	T/℃	Base	Yield/%
1	I	PhCF₃	50	Cs₂CO₃	25
2	I	DCE	50	Cs₂CO₃	47
3	I	MeCN	50	Cs₂CO₃	50
4	I	THF	50	Cs₂CO₃	20
5	I	DMF	50	Cs₂CO₃	24
6	I	DMAc	50	Cs₂CO₃	15
7	II	MeCN	50	Cs₂CO₃	73
8	III	MeCN	50	Cs₂CO₃	87
9	IV	MeCN	50	Cs₂CO₃	15
10	V	MeCN	50	Cs₂CO₃	32
11	III	MeCN	50	K₂CO₃	93
12	III	MeCN	50	KHCO₃	82
13	III	MeCN	50	K₂HPO₄	79
14	III	MeCN	50	KH₂PO₄	91
15	III	MeCN	50	Cs₂CO₃	88
16	III	MeCN	50	CsF	80
17	III	MeCN	50	K₃PO₄	85
18	III	MeCN	50	—	99
19	III	MeCN	r.t.	—	76

表1. 2-位取代吲哚去芳构化反应的条件筛选a

Table 1. Condition screening for dearomatization of 2-substi- tuted indoles

表2. 2-位取代吲哚底物拓展a

Table 2. Substrate scope of 2-substituted indoles

Entry	PC	Yield/%
1	III	40
2	I	95
3	II	2
4	IV	43
5	V	60

表3. 2-位非取代吲哚去芳构化反应的条件筛选a

Table 3. Condition screening for dearomatization of 2-unsubstituted indole

表4. 2-位非取代吲哚底物拓展a

Table 4. Substrate scope of 2-unsubstituted indole

图式2. 放大量实验和合成转化实验

Scheme 2. Large-scale synthesis and synthetic transfo rmations

图式3. 控制实验

Scheme 3. Control experiments

图2. (a)开/关灯实验和(b) 荧光淬灭实验

Figure 2. (a) Light on/off experiments and (b) Stern-Volmer quenching studies

图式4. 可能的反应机理(吉布斯自由能单位: kJ/mol)

Scheme 4. Proposed mechanism (Gibbs free energies are given in kJ/mol)

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