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化学进展 2021, Vol. 33 Issue (11): 1947-1952 DOI: 10.7536/PC201001 前一篇   后一篇

• 综述 •

C—H氰烷基化:导向基控制的萘酰亚胺C—H氰烷基化

陈曦, 李喆垚, 陈亚运, 陈志华, 胡艳, 刘传祥*()   

  1. 上海应用技术大学化学与环境工程学院 上海 201418
  • 收稿日期:2020-10-09 修回日期:2021-01-14 出版日期:2021-11-20 发布日期:2021-03-04
  • 通讯作者: 刘传祥
  • 基金资助:
    上海市科学技术委员会(17ZR1429900); 上海市化学生物学重点实验室开放基金资助
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C—H Cyanoalkylation:the Direct C—H Cyanomethylation of Naphthalimide

Xi Chen, Zheyao Li, Yayun Chen, Zhihua Chen, Yan Hu, Chuanxiang Liu()   

  1. School of Chemical and Environmental Engineering, Shanghai Institute of Technology,Shanghai 201418, China
  • Received:2020-10-09 Revised:2021-01-14 Online:2021-11-20 Published:2021-03-04
  • Contact: Chuanxiang Liu
  • Supported by:
    Natural Science Foundation of Shanghai(17ZR1429900); Opening Fund of Shanghai Key Laboratory of Chemical Biology.

氰基广泛存在药物活性分子中,且氰基可以很容易转化成酰胺、酯基、醛基以及伯胺等官能团,因此有机分子的氰烷基/甲基化反应得到有机和药学研究者的广泛关注。尽管已有合成策略可以选择性引入氰基,近年来最有效的方法是通过C—H键激活直接与乙腈或取代乙腈发生氰甲基/氰烷基化反应,因其具有高效的原子经济性以及可规避预官能团化等优点。因此,本文详细评述了自由基促进的氰甲基化、光化学催化直接氰甲基化、芳环或杂环脱氢偶联氰甲基化、导向基促进的氰甲基化、本课题组发展的荧光团(Fluorophore C—H)直接氰甲基化反应的研究进展。

关键词： 氰甲基化, C—H功能化, 自由基, 导向基, 萘酰亚胺

The cyanoalkylation/cyanomethylation of organic molecules is of great research interest to organic and medicinal chemists due to the wide presence of the cyano group in biologically active molecules and the facile conversion of the cyano group into many other functional groups, such as amides, esters, aldehydes, and primary amines. Although a variety of different synthetic strategies have been developed for the selective introduction of the cyanomethyl group, an attractive approach is to use acetonitrile directly through C—H activation due to the highly efficient atom economy and the avoidance of prefunctionalization. Therefore, this review summarizes the main research progress in C—H cyanoalkylation/cyanomethylation of radical cyanomethylation, Photochemical Cross-coupling reaction, Cross-Dehydrogenative Coupling(CDC) Reaction, Directing group-promoted C—H cyanomethylation and Fluorophore C—H cyanomethylation reported by our group.

Contents

1 Introduction

2 Radical cyanomethylation of activated alkenes with acetonitrile

3 Photochemical cross-coupling reaction of alkene or aroma C(sp2)—H functionalization of acetonitrile

4 Cross-dehydrogenative coupling(CDC) reaction of aromatic ring C(sp2)—H functionalization of acetonitrile

5 Directing group-promoted C—H cyanomethylation

6 Conclusion and outlook

Key words: cyanomethylation, C—H functionalization, radical, directing group, naphthalimide
()
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