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2022 , Vol. 42 >Issue 2: 391 - 423

DOI: https://doi.org/10.6023/cjoc202108012

综述与进展

铑(III)催化的C(sp3)—H官能团化

  • 韩高旭 ,
  • 许红涛 ,
  • 侯卫
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  • a 浙江工业大学药学院 新药开发与化学生物学研究所 杭州 310014
    b 上海科技大学免疫化学研究所 上海 201210

收稿日期: 2021-08-10

  修回日期: 2021-09-22

  网络出版日期: 2022-02-24

基金资助

国家自然科学基金(21907085)

收起

Rhodium(III) Catalyzed C(sp3)—H Functionalization

  • Gaoxu Han ,
  • Hongtao Xu ,
  • Wei Hou
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  • a Institute of Drug Development & Chemical Biology, College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014
    b Shanghai Institute for Advanced Immunochemical Studies, ShanghaiTech University, Shanghai 201210
* Corresponding authors. E-mail: ;

Received date: 2021-08-10

  Revised date: 2021-09-22

  Online published: 2022-02-24

Supported by

National Natural Science Foundation of China(21907085)

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摘要

三价铑的外层电子为d6, 非常缺电子. 因此, Rh(III)催化C—H活化形成的C—Rh(III)键极性大,可以与多种包含极性键的试剂发生末端反应, 从而与钯等金属形成良好的交叉互补. 近年来, Rh(III)催化的C(sp2)—H键的官能团化反应取得了长足的发展, 在杂环骨架构建、药物修饰等方面应用越来越频繁. 惰性的C(sp3)—H键与C(sp2)—H键的活化机制类似,但是C(sp3)—H键的键能比C(sp2)—H键更强,并且没有易与金属中心发生轨道相互作用的π电子, 使该领域的探索和研究依然面临艰巨的挑战. 根据不同的反应类型进行分类, 系统地概括了Rh(III)催化C(sp3)—H键官能团化这一领域的研究进展.

关键词： 铑(III); C(sp3)—H官能团化; 烷基化; 芳基化; 羰基化; 烯基化; 胺化; 环化

本文引用格式

韩高旭 , 许红涛 , 侯卫 . 铑(III)催化的C(sp3)—H官能团化[J]. 有机化学, 2022 , 42(2) : 391 -423 . DOI: 10.6023/cjoc202108012

Abstract

The outer electron of trivalent rhodium is d6, which is very electron deficient. Therefore, the C—Rh(III) bond formed by Rh(III) catalyzed C—H activation is of big polarity and can react with a variety of terminal reagents containing polar bonds, thus forming a good cross complementarity with palladium and other metals. In recent years, significant progress has been made in the Rh(III) catalyzed C(sp2)—H bond functionalization. And many of the reported methods have been applied in heterocyclic skeleton construction and drug modification more and more frequently. Although the activation mechanism of inert C(sp3)—H bond is similar to that of C(sp2)—H bond, the bond energy of C(sp3)—H bond is more stronger, and there is no π electron easily to interact with the metal center, so the exploration and research in this field still face arduous challenges. The research progress in Rh(III) catalyzed C(sp3)—H functionalization is systematically summarized and the reported work is classified into different reaction types.

Key words： rhodium(III); C(sp3)—H functionalization; alkylation; arylation; carbonylation; alkenylation; amination; cyclization

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