α-氧代羧酸、炔和伯胺的多组分碳氢环化构筑异喹啉鎓骨架

doi:10.6023/cjoc202507007

研究论文

α-氧代羧酸、炔和伯胺的多组分碳氢环化构筑异喹啉鎓骨架

曾依玲^a, 梁方鹏^a, 李辉^a, 刘荣荣^a, 李世清^a,*

^a广西电化学与磁化学功能材料重点实验室,桂林理工大学化学与生物工程学院桂林 541004

收稿日期:2025-07-04 修回日期:2025-09-22
基金资助:
国家自然科学基金(Nos. 22261013, 22001049)、广西自然科学基金(No. 2020GXNSFBA297003)资助项目.

Multi-Component C-H Annulation of α-Oxocarboxylic Acids, Allynes and Primary Amines to Yield Isoquinolinium Skeletons

Zeng Yiling^a, Liang Fangpeng^a, Li Hui^a, Rongrong Liu^a, Li Shiqing^a,*

^aGuangxi Key Laboratory of Electrochemical and Magneto-Chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, China

Received:2025-07-04 Revised:2025-09-22
Contact: * E-mail: lisq@glut.edu.cn
Supported by:
Project supported by grants from the National Natural Science Foundation of China (Nos. 22261013, 22001049), and Guangxi Natural Science Foundation (No. 2020GXNSFBA297003).

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摘要/Abstract

本研究开发了Rh(III) 催化α-氧代羧酸、炔和伯胺等三组分C-H键活化/环化反应,一步构筑二、四并环的异喹啉鎓盐衍生物。伯胺与α-氧代羧酸通过酮胺缩合原位生成α-亚胺酸,从而将α-氧代羧酸的弱氧导向转变成强氮导向。当烷基胺为氮源时,α-亚胺酸与炔烃发生氮导向的C-H键活化/环化反应,以较高的产率得到二并环的N-烷基异喹啉鎓盐（离子液）。当芳胺作为氮源时,α-亚胺酸与炔烃发生氮导向的C-H环化后可以进一步发生羧基导向的C-H键活化/环化反应,从而以中等至较好的产率得到四并环的二苯并[a,f]喹嗪鎓盐。通过时间依赖的ESI-MS成功检测到7个关键中间体,其中包括3个羧基保留的物种,证明了羧基在该反应中的重要性,并以此提出包含了酮胺缩合、脱羧、C-H键活化、炔烃插入及还原消除等过程的反应机理。

关键词: α-氧代羧酸, C-H键活化/环化, 多组分, 铑催化, 异喹啉鎓

This study reports the Rh(III)-catalyzed three-component C-H activation/annulation reaction of α-oxocarboxylic acids, alkynes, and primary amines to construct bicyclic and tetracyclic isoquinolinium derivatives. The in-situ generated α-imino acid intermediates from keto-amine condensation betweenα-oxocarboxylic acid and primary amine enables a directing group switch from weak oxygen to strong nitrogen. By using alkylamines as N-source, N-directed C-H activation of α-imino acids and alkynes afford bicyclic N-alkyl isoquinolinium salts (ionic liquids) in high yields. When using arylamines instead, the sequential N- and carboxyl-directed C-H activation/annulation process furnish tetracyclic dibenzo[a,f]quinolizinium salts with moderate to good yields. Seven key intermediates, including three carboxylate-retained species, have been characterized by time-dependent ESI-MS analysis, supporting a plausible mechanism involving keto-amine condensation, decarboxylation, C-H activation, alkyne insertion, and reductive elimination.

Key words: α-oxocarboxylic acids, C-H activation/annulation, multi-component, rhodium-catalysis, isoquinolinium

引用此文

曾依玲, 梁方鹏, 李辉, 刘荣荣, 李世清. α-氧代羧酸、炔和伯胺的多组分碳氢环化构筑异喹啉鎓骨架[J]. 有机化学, doi: 10.6023/cjoc202507007.

Zeng Yiling, Liang Fangpeng, Li Hui, Rongrong Liu, Li Shiqing. Multi-Component C-H Annulation of α-Oxocarboxylic Acids, Allynes and Primary Amines to Yield Isoquinolinium Skeletons[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202507007.

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