高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (2): 254-260.doi: 10.7503/cjcu20150716

• 有机化学 • 上一篇    下一篇

无金属参与的二乙酸碘苯促进吲哚C3—H乙酸化反应

王亮1,2(), 瞿星1, 李站1, 顾昌翰1, 胡思前1,2()   

  1. 1. 江汉大学光电化学材料与器件教育部重点实验室, 武汉 430056
    2. 化学与环境工程学院, 武汉 430056
  • 收稿日期:2015-09-14 出版日期:2016-02-10 发布日期:2016-01-04
  • 作者简介:联系人简介: 王 亮, 男, 博士, 讲师, 主要从事杂环化合物的C—H官能化研究. E-mail:wangliang@jhun.edu.cn;胡思前, 男, 教授, 主要从事杂环导向的有机功能材料研究. E-mail:husiqian@126.com
  • 基金资助:
    国家自然科学基金(批准号: 21302064)、 湖北省教育厅科学研究计划指导性项目(批准号: B2015231)和江汉大学博士科研启动经费项目(批准号: 2012023)资助

Metal-free C3—H Acetoxylation of Indoles Promoted by PhI(OAc)2

WANG Liang1,2,*(), QU Xing1, LI Zhan1, GU Changhan1, HU Siqian1,2,*()   

  1. 1. Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, Jianghan University, Wuhan 430056, China
    2. School of Chemical and Enviromental Engineering, Jianghan University, Wuhan 430056, China
  • Received:2015-09-14 Online:2016-02-10 Published:2016-01-04
  • Contact: WANG Liang,HU Siqian E-mail:wangliang@jhun.edu.cn;husiqian@126.com
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21302064), the Scientific Research Project of Hubei Provincial Department of Education, China(No.B2015231) and the Scientific Research Initial Funds for Doctors of Jianghan University, China(No.2012023)

摘要:

研究了无金属参与的二乙酸碘苯和吲哚的C3—H乙酸化反应, 通过对取代基效应、 温度以及二乙酸碘苯用量等因素的考察, 建立了反应的最佳条件: 反应温度60 ℃, 乙酸(HOAc)为溶剂. 在无需任何添加剂条件下, 以中等到良好的收率获得一系列C3位乙酸化的吲哚衍生物. 采用红外光谱、 核磁共振波谱、 高分辨质谱及X射线单晶衍射分析对目标化合物进行了结构表征, 并推测了可能的反应机理. 该催化体系对于克量级规模反应均能获得很好的结果.

关键词: 无金属, 二乙酸碘苯, 吲哚, 乙酸化

Abstract:

3-Substituted indoles are common structural motifs in a series of natural products, pharmaceuticals and biologically active compounds. Metal-free reaction was emerged as one of the most powerful tools for functionalization of indoles due to its environment friendly features. In this work, the metal-free C3—H acetoxylation of indoles and PhI(OAc)2 was developed. The optimized reaction conditions were established by examination of the substituent, temperature and amounts of PhI(OAc)2. A series of 3-acetoxyindoles could be obtained in HOAc at 60 ℃ without additives. The yield of product ranged from 45% to 86%. The structures were characterized by infrared(IR), nuclear magnetion resonance(NMR), high resolution mass spectra(HRMS) and X-ray diffraction techniques and a possible reaction mechanism was then proposed. Moreover, this reaction system was also feasible in a gram-scale reaction without significant decrease in the product yields.

Key words: Metal-free, Diacetoxyiodobenzene, Indole, Acetoxylation

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