有机化学 ›› 2025, Vol. 45 ›› Issue (7): 2367-2388.DOI: 10.6023/cjoc202410023 上一篇    下一篇

综述与进展

基于C—OMe键断裂的芳甲醚转化反应研究进展

沈一鸣a, 邹东b,*()   

  1. a 浙江大学医学院附属第二医院药学部 杭州 310009
    b 浙江大学医学院附属邵逸夫医院药学部 杭州 310016
  • 收稿日期:2024-10-29 修回日期:2024-11-29 发布日期:2025-01-17

Recent Advances in the Transformation Reactions of Aryl Ethers via C—OMe Bond Cleavage

Yiming Shena, Dong Zoub,*()   

  1. a Department of Pharmacy, The Second Affiliated Hospital Zhejiang University School of Medicine, Hangzhou 310009
    b Department of Pharmacy, Sir Run Run Shaw Hospital, Zhejiang University School of Medicine, Hangzhou 310016
  • Received:2024-10-29 Revised:2024-11-29 Published:2025-01-17
  • Contact: *E-mail: zoudong16@zju.edu.cn

芳基卤化物是金属催化偶联反应最常用的亲电试剂之一, 因其合成成本较高, 且参与反应时会产生化学计量的卤化物肥料, 因此开发更持续、环保的芳基卤化物替代物成为近年研究热点之一. 尽管前期已实现了一些基于苯酚衍生物的交叉偶联, 例如芳基磺酸盐、芳基酯或芳基氨基甲酸酯等, 但含硫废物的产生, 加上高昂的价格, 使得此类物质的应用前景大大降低. 芳甲醚是一类基础且重要的原料和中间体, 也是苯酚的最简单衍生物, 商业可购且价格低廉, 并且甲氧基的离去几乎不会对环境造成任何污染. 因此, 开发简便、高效的方法催化芳甲醚转化反应具有重要研究意义. 综述了近十年基于C—OMe键断裂的芳甲醚转化反应研究进展, 并按照不同反应原理分类, 包括过渡金属催化的C—OMe键转化和无过渡金属催化/介导的C—OMe键转化(自由基介导的C—OMe键转化和Brønsted酸/碱催化的C—OMe键转化), 并详细论述了反应条件、底物耐受性、反应机理、应用与不足等.

关键词: 芳甲醚, 芳基卤化物替代物, C—OMe键断裂, 转化反应

Aryl halides are one of the most commonly used electrophilic reagents for metal-catalyzed coupling reactions. Due to their high synthesis cost and the production of stoichiometric halide fertilizers when participating in the reaction, the development of more sustainable and environmentally friendly alternatives to aryl halides has become one of the hot topics of research in recent years. Although cross-coupling of several phenol derivatives, which including aryl sulfonates, aryl esters and aryl carbamates, has been achieved in the past, the generation of sulfur-containing waste, coupled with high prices, has greatly reduced the application prospects of such substances. Aryl ethers are a basic and important class of raw materials and intermediates, as well as the simplest derivative of phenol. They are commercially available and inexpensive, and the absence of methoxy groups hardly causes any pollution to the environment. Therefore, it is of great significance to develop simple and efficient methods for catalytic conversion of aryl methyl ethers. Herein, we comprehensively summarize the research progress in the transformation reactions of aryl ethers via C—OMe bond cleavage in the past decade and classify them according to different reaction principles, including transition-metal catalyzed C—OMe bond transformation and transition-metal-free catalyzed/mediated C—OMe bond transformation (radical-mediated C—OMe bond transformation and Brønsted acid/base catalyzed C—OMe bond transformation). The reaction conditions, substrate tolerance, reaction mechanism, applications, and shortcomings are discussed in detail.

Key words: aryl ethers, aryl halide substitutes, C—OMe bond cleavage, transformation reactions