高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (2): 241.doi: 10.7503/cjcu20170374

• 有机化学 • 上一篇    下一篇

可见光诱导对位苯酚/苯胺邻位多氟烷基化

袁莉, 李增增, 蒋圣明, 朱勇, 夏绿露, 李岚, 赵传奇, 蒋婷, 雷千, 唐石()   

  1. 吉首大学化学化工学院, 武陵山地区民族药解析与创制湖南省工程实验室, 吉首 416000
  • 收稿日期:2017-06-12 出版日期:2018-02-10 发布日期:2017-12-23
  • 作者简介:联系人简介: 唐 石, 男, 博士, 副教授, 主要从事有机催化合成方面的研究. E-mail: stang@jsu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21462017, 21662013)、 湖南省教育厅项目(批准号: 16A171)和湖南省研究生科研创新项目(批准号: CX2017B709)资助

Visible-light-induced ortho-Perfluoroalkylation of para-Substituted Phenols and Anilines

YUAN Li, LI Zengzeng, JIANG Shengming, ZHU Yong, XIA Lülu, LI Lan, ZHAO Chuanqi, JIANG Ting, LEI Qian, TANG Shi*()   

  1. Engineering Laboratory for Analysis and Drugs Development of Ethnomedicinein Wuling Mountains,College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, China
  • Received:2017-06-12 Online:2018-02-10 Published:2017-12-23
  • Contact: TANG Shi E-mail:stang@jsu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21462017, 21662013), the Scientific Research Fund of Hunan Provincial Education Department, China(No.16A171) and the Research Innovation Program for Graduates in Hunan Province, China(No;CX2017B709)

摘要:

发展了一种简便、 清洁的可见光催化的苯酚/苯胺邻位多氟烷基化反应路线. 以较廉价的多氟烷基碘或溴为自由基源, Ru(bpy)3Cl2为催化剂, 在LED蓝光灯照射下, 多种对位取代的苯酚/苯胺高效选择性地发生邻位多氟烷基化反应, 以80%~92%的产率合成了一系列多氟烷基化的芳香化合物. 此反应在无需保护基团的情况下, 可快速在游离苯酚/苯胺类化合物骨架上引入CF3, C3F7, C4F9, C6F13, C8F17I和CF2CO2Et等一系列多氟烷基基团. 此反应条件温和(室温)、 催化体系绿色, 为具有潜在药用价值和生理活性的含氟苯酚/苯胺类芳香族化合物的合成提供了一条高效、 快捷的新途径.

关键词: 光催化, 邻位多氟烷基化, 苯酚, 芳香胺

Abstract:

A simple, clean visible-light-induced ortho-selective perfluoroalkylation of various phenols/anilines was developed. Using economic bromides/iodidesas as radical source and Ru(bpy)3Cl2 as catalyst, a series of para-substituted phenols/anilines underwent perfluoroalkylation efficiently under the irradiation of blue LEDs, leading to various perfluoroalkylated arenes in 80%—92% yields. Notably, various of perfluorinated moieties including C3F7, C4F9, C6F13, C8F17 and CF2CO2Et were incorporated efficiently into the phenols/aniline motifs without the protecting groups on the N/O-atom. The reaction proceeded under mild condition(room temperature) and green catalytic system. Arguably, it provides an effective and quick approach to fluoro-contained phenols/anilines with pharmaceutical value and biological activity.

Key words: Visible-light-induced, ortho-Perfluoroalkylation, Phenols, Aromatic anline

TrendMD: