BF3•OEt2介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物

doi:10.6023/cjoc202403041

有机化学 ›› 2024, Vol. 44 ›› Issue (9): 2785-2795.DOI: 10.6023/cjoc202403041 上一篇下一篇

研究论文

BF₃•OEt₂介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物

高宇珅^a^,^b, 高媛媛^b, 张安安^b, 李路^b, 耿巍芝^c, 张凤华^a^,^*(), 李飞^a^,^*(), 刘澜涛^a^,^b^,^*()

a 辽宁石油化工大学石油化工学院辽宁抚顺 113001
b 商丘师范学院化学化工学院河南省药物绿色合成工程研究中心河南商丘 476000
c 新乡润宇材料有限公司河南新乡 453000

收稿日期:2024-03-26 修回日期:2024-05-08 发布日期:2024-05-30
通讯作者: 张凤华, 李飞, 刘澜涛
基金资助:
河南省自然科学基金(232300421234); 河南省高校重点科研项目(24B150027); 河南省高校重点科研项目(24A530007); 商丘市科技创新领军人才(SQRC202212004); 商丘师范学院(黄河故道区生态环境保护计划)

BF₃•OEt₂ Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles

Yushen Gao^a^,^b, Yuanyuan Gao^b, An'an Zhang^b, Lu Li^b, Weizhi Geng^c, Fenghua Zhang^a(), Fei Li^a(), Lantao Liu^a^,^b()

a School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun, Liaoning 113001
b Henan Engineering Research Center of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000
c Xinxiang Runyu Material Co. Ltd., Xinxiang, Henan 453000

Received:2024-03-26 Revised:2024-05-08 Published:2024-05-30
Contact: Fenghua Zhang, Fei Li, Lantao Liu
Supported by:
Natural Science Foundation of Henan Province(232300421234); Key Scientific Research Project of Colleges and Universities in Henan Province(24B150027); Key Scientific Research Project of Colleges and Universities in Henan Province(24A530007); Leading Talents in Scientific and Technological Innovation in Shangqiu City(SQRC202212004); Shangqiu Normal University(Program of Ecological Environmental Protection in the Area of Old Course of Yellow River)

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摘要/Abstract

3-硫醚吲哚广泛存在于天然产物、生物活性分子和有机功能材料中. 报道了一种非金属催化条件下BF₃•OEt₂介导的2-炔基苯胺与N-(芳基硫)琥珀酰亚胺的亲电环化反应, 高效合成了一系列3-硫醚吲哚衍生物. 该方案具有适用范围广、官能团兼容性好、条件温和及操作简便等优点. 此外, 克级反应也证明了该方法具有良好的应用前景.

关键词: 2-炔基苯胺, 亲电环化, 非金属催化, 3-硫醚吲哚

3-Sulfenylindoles are widely found in natural products, bioactive molecules and organic functional materials. BF₃•OEt₂ mediated electrophilic cyclization reaction of 2-alkynylaniline with N-(arylthio)succinimide was developed leading to the efficient synthesis of various biologically active 3-sulfenylindoles in moderate to high yields under very mild conditions. This protocol has the advantages of broad scope, functional group diversity, mild conditions and ease of operation. Moreover, gram-scale preparation portends the practical application.

Key words: 2-alkynylaniline, electrophilic cyclization, metal-free catalysis, 3-sulfenylindole

引用此文

高宇珅, 高媛媛, 张安安, 李路, 耿巍芝, 张凤华, 李飞, 刘澜涛. BF₃•OEt₂介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物[J]. 有机化学, 2024, 44(9): 2785-2795.

Yushen Gao, Yuanyuan Gao, An'an Zhang, Lu Li, Weizhi Geng, Fenghua Zhang, Fei Li, Lantao Liu. BF₃•OEt₂ Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2785-2795.

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图/表 8

Figure 1. Bioactive compounds of 3-sulfenylindoles

Scheme 1. 3-Sulfenylindole synthesis strategies

Entry	BF₃•OEt₂/mol%	Dosage/equiv. of 1a/2a	T/℃	Solvent	Yield^b/%
1	10	1/1.2	30	DCM	35
2	20	1/1.2	30	DCM	78
3	30	1/1.2	30	DCM	89
4	20	1/1.5	30	DCM	98
5	20	1/1.5	30	Toluene	17
6	20	1/1.5	30	THF	Trace
7	20	1/1.5	30	CH₃CN	Trace
8	20	1/1.5	30	DCE	98
9^c	20	1/1.5	40	DCE	99
10^d	20	1/1.5	50	DCE	99

Table 1. Optimization of reaction conditionsa

Table 2. Scope of 2-alkynylanilines derivativesa

Table 3. Scope of sulfur source a

Scheme 2. Gram-scale synthesis

Scheme 3. Control experiments

Scheme 4. Proposed reaction mechanism

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BF₃•OEt₂介导2-炔基苯胺的分子内环化反应合成3-硫醚吲哚化合物

BF₃•OEt₂ Mediated Intramolecular Cyclization of 2-Alkynylanilines Approach to 3-Sulfenylindoles

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