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2021 , Vol. 41 >Issue 11: 4476 - 4483

DOI: https://doi.org/10.6023/cjoc202106017

研究论文

三价铑催化通过环己二酮高效构建异香豆素类化合物

  • 戴雨倩 ,
  • 李兴伟 ,
  • 刘丙贤
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  • 河南师范大学化学化工学院 国家药监局创新药物研究与评价重点实验室 河南省精细化工绿色生产协同创新中心 河南新乡 453007

收稿日期: 2021-06-08

  修回日期: 2021-07-13

  网络出版日期: 2021-07-26

基金资助

国家自然科学基金(21801066); 国家自然科学基金(21525208); 国家自然科学基金(U1804283); 国家自然科学基金(21801067); 国家博士后科学基金(2020M682307); 国家博士后科学基金(2021T140183)

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Rh(III)-Catalyzed Efficient Synthesis of Isocoumarins from Cyclohexanediones

  • Yuqian Dai ,
  • Xingwei Li ,
  • Bingxian Liu
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  • NMPA Key Laboratory for Research and Evaluation of Innovative Drug, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007
* Corresponding author. E-mail:

Received date: 2021-06-08

  Revised date: 2021-07-13

  Online published: 2021-07-26

Supported by

National Natural Science Foundation of China(21801066); National Natural Science Foundation of China(21525208); National Natural Science Foundation of China(U1804283); National Natural Science Foundation of China(21801067); China Postdoctoral Science Foundation(2020M682307); China Postdoctoral Science Foundation(2021T140183)

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摘要

异香豆素结构是一类重要的天然产物及活性分子骨架, 发展其简便高效的合成方法具有重要的意义. 本工作通过过渡金属铑催化芳烃C—H键活化并与原位生成的环己二酮碘叶立德类化合物发生环化反应, 一锅法构建环己酮并异香豆素骨架结构. 不同的定位基团在该反应体系下均可以顺利发生反应, 其中亚砜叶立德及苯甲酸类化合物表现出良好的活性, 可以高效地实现目标产物的合成. 对照实验、氘标记实验以及中间体分离等机理实验说明反应过程碘叶立德中间体的生成对反应发生具有重要作用.

关键词： 异香豆素; 碘叶立德; 碳氢键活化; 铑催化

本文引用格式

戴雨倩 , 李兴伟 , 刘丙贤 . 三价铑催化通过环己二酮高效构建异香豆素类化合物[J]. 有机化学, 2021 , 41(11) : 4476 -4483 . DOI: 10.6023/cjoc202106017

Abstract

Isocoumarin skeleton is a kind of important motif of natural product and bio-active molecular. The synthesis of simple and efficient construction of isocoumarin is of great significance. This work realized the one-pot synthesis of cyclohexanone-isocoumarins by rohdium catalyzed aryl C—H activation and followed annulation with in-situ generated iodonium ylides of cyclohexanones. Divers directing groups can be tolerated under the system leading to the desired products, among which sulfoxonium ylides and benzoic acids exhibited good reaction efficiency. Control experiments, deuterium labeling experiments and isolation of the possible intermediate revealed that the in-situ generated iodonium ylides were necessary for the reaction system.

Key words： isocoumarins; iodonium ylides; C—H activation; Rh-catalysis

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