钴催化2-芳基吲哚氧化去芳构化及与烯酰胺[3+2]环化反应

doi:10.6023/cjoc202104057

摘要/Abstract

在氧气氛围中, 以2-芳基吲哚和N-乙酰基烯胺为原料, 实现了一锅法快速构建三环吲哚啉稠环骨架化合物. 该方法具有原料易得、操作简便、区域和非对映选择性较高以及环境友好等特点. 机理研究表明, 反应首先发生氧化去芳构化, 随后与烯酰胺进行[3+2]环化反应.

关键词: 钴催化, 氧化去芳构化, 环化反应, 吲哚, 烯酰胺

An one-pot reaction for the rapid construction of tricyclic fused indoline frameworks from 2-aryl indoles and N-acetyl enamides under oxygen atmosphere has been developed. The notable features of this method involve easy availability of starting materials, simple manipulation, good regio- and diastereo-selectivity, as well as environmentally friendly conditions. Mechanistic studies indicated that this reaction proceeds via oxidative dearomatization and subsequent [3+2] annulation with enamides.

Key words: cobalt-catalysis, oxidative dearomatization, annulation, indoles, enamides

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黄音君, 李金山, 李珅, 马军安. 钴催化2-芳基吲哚氧化去芳构化及与烯酰胺[3+2]环化反应[J]. 有机化学, 2021, 41(10): 4028-4038.

Yinjun Huang, Jinshan Li, Shen Li, Junan Ma. Cobalt-Catalyzed Aerobic Oxidative Dearomatization of 2-Aryl Indoles and in situ [3+2] Annulation with Enamides[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 4028-4038.

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图/表 7

Scheme 1. Oxidative dearomatization-triggered annulation of indoles

Entry	Catalyst	Solvent	Time/h	Yield^b/%	dr^c
1	Co(salophen)	CH₂Cl₂	48	72	4∶1
2	Co(TPP)	CH₂Cl₂	24^d	72	4∶1
3	Co(TPP)	CHCl₃	6^e	82	4∶1
4	Co(TPP)	CCl₄	12^f	64	4∶1
5	Co(TPP)	DCE	48	28	4∶1
6	Co(TPP)	Et₂O	48	10	2∶1
7	Co(TPP)	THF	48	34	5∶1
8	Co(TPP)	Toluene	48	25	4∶1

Table 1. Condition optimizationa

Table 2. Substrate scope with respect to 2-aryl 1H-indolesa

Table 3. Substrate scope with respect to N-acetyl enamidesa

Scheme 2. Gram-scale reaction and synthetic application

Scheme 3. Control experiments

Scheme 4. Proposed mechanism

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