金属引导的发散型傅-克环化反应合成羰基稠合的吲哚/吡咯

doi:10.6023/cjoc202105021

有机化学 ›› 2021, Vol. 41 ›› Issue (9): 3521-3531.DOI: 10.6023/cjoc202105021 上一篇下一篇

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金属引导的发散型傅-克环化反应合成羰基稠合的吲哚/吡咯

罗和江^a, 曹同祥^a^,^*(), 祝诗发^a^,^b^,^*()

a 华南理工大学化学与化工学院广东省功能分子工程重点实验室广州 510640
b 中新国际合作研究院广州 510555

收稿日期:2021-05-11 修回日期:2021-06-03 发布日期:2021-06-07
通讯作者: 曹同祥, 祝诗发
基金资助:
中华人民共和国科技部(2016YFA0602900); 国家自然科学基金(21871096); 国家自然科学基金(22071062); 国家自然科学基金(22001077); 广东省科学技术基金(2018B030308007); 广东省科学技术基金(2018A030310359); 广东省科学技术基金(2021A1515012331); 中国博士后科学基金(2018M643062); 中国博士后科学基金(2019T120723)

Divergent Synthesis of Ketone-Fused Indoles/Pyrroles via Metal-Guided Friedel-Crafts Cyclization

Hejiang Luo^a, Tongxiang Cao^a(), Shifa Zhu^a^,^b()

a Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640
b China-Singapore International Joint Research Institute, Guangzhou 510555

Received:2021-05-11 Revised:2021-06-03 Published:2021-06-07
Contact: Tongxiang Cao, Shifa Zhu
Supported by:
Ministry of Science and Technology of the People's Republic of China(2016YFA0602900); National Natural Science Foundation of China(21871096); National Natural Science Foundation of China(22071062); National Natural Science Foundation of China(22001077); Guangdong Provincal Science and Technology Fund(2018B030308007); Guangdong Provincal Science and Technology Fund(2018A030310359); Guangdong Provincal Science and Technology Fund(2021A1515012331); China Postdoctoral Science Foundation(2018M643062); China Postdoctoral Science Foundation(2019T120723)

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摘要/Abstract

报道了金属引导由N-(2-炔基芳基)内酰胺发散型合成羰基稠合的吲哚/吡咯的方法. 该反应通过可调控的酰基正离子区域选择性傅-克环化反应进行, 同时具有底物范围广, 原子经济性和步骤经济性高等优势, 有望用于含有相关结构的生物活性分子的合成.

关键词: 傅-克环化反应, 羰基稠合的吲哚/吡咯, 发散型合成

A metal-guided method for divergent synthesis of ketone-fused indoles/pyrroles from N-(2-alkynylaryl) lactam is described. The reaction is proposed to proceed through a regioswitchable Friedel-Crafts cyclization of acylium. The obvious advantages are wide substrate scopes, high atom economy and step economy, which have a great potential in the synthesis of structure-related bioactive compounds.

Key words: Friedel-Crafts cyclization, ketone-fused indoles/pyrroles, divergent synthesis

引用此文

罗和江, 曹同祥, 祝诗发. 金属引导的发散型傅-克环化反应合成羰基稠合的吲哚/吡咯[J]. 有机化学, 2021, 41(9): 3521-3531.

Hejiang Luo, Tongxiang Cao, Shifa Zhu. Divergent Synthesis of Ketone-Fused Indoles/Pyrroles via Metal-Guided Friedel-Crafts Cyclization[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3521-3531.

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图/表 8

Scheme 1. Indole/pyrrole containing natural or bioactive compounds

Scheme 2. Metal-guided selective Friedel-Crafts cyclization

Entry	Cat. (mol%)	Temp./℃	Yield/%
Entry	Cat. (mol%)	Temp./℃	2a	3a
1	AgSbF₆ (5)	80	15	ND
2	IPrAuNTf₂ (5)	80	45	43
3	Hg(OTf)₂ (5)	80	41	ND
4	AgSbF₆ (5)	Reflux	21	ND
5	AgNTf₂ (5)	Reflux	28	ND
6	AgNTf₂ (10)	Reflux	48	ND
7	AgNTf₂ (20)	Reflux	72^b	ND
8	Hg(OTf)₂ (10)	60	61	ND
9	PdCl₂ (10)	Reflux	16	53^b
10	Pd(PhCN)₂Cl₂ (10)	Reflux	11	34
11	Pd(cod)Cl₂ (10)	Reflux	12	43
12	Pd(PPh₃)₄ (10)	Reflux	39	ND
13	—	Reflux	ND	ND

Table 1. Optimization of the reaction conditionsa

Table 2. Substrate scope with AgNTf2 as the catalysta

Table 3. Substrate scope with PdCl2 as the catalysta

Scheme 3. Chemical transformation of 2a

Scheme 4. Active acylium intermediate trapping experiemts

Scheme 5. Proposed reaction mechanism of divergent Friedel-Crafts cyclization

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金属引导的发散型傅-克环化反应合成羰基稠合的吲哚/吡咯

Divergent Synthesis of Ketone-Fused Indoles/Pyrroles via Metal-Guided Friedel-Crafts Cyclization

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