有机化学 ›› 2020, Vol. 40 ›› Issue (11): 3881-3888.DOI: 10.6023/cjoc202006075 上一篇    下一篇

所属专题: 有机硅化学合辑

研究论文

钯催化芳香溴化物与三甲基硅基重氮甲烷的还原偶联及其在芳香化合物甲基化中的应用

王帅, 杨成, 孙硕, 孙晗力, 王剑波   

  1. 北京大学化学与分子工程学院 生物有机与分子工程教育部重点实验室 北京 100871
  • 收稿日期:2020-06-30 修回日期:2020-07-19 发布日期:2020-08-06
  • 通讯作者: 王剑波 E-mail:wangjb@pku.edu.cn
  • 基金资助:
    国家自然科学基金(No.91956104)资助项目.

Palladium-Catalyzed Reductive Coupling of Aromatic Bromides and Trimethylsilyldiazomethane: Its Application to Methylation of Aromatic Compounds

Wang Shuai, Yang Cheng, Sun Shuo, Sun Hanli, Wang Jianbo   

  1. Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
  • Received:2020-06-30 Revised:2020-07-19 Published:2020-08-06
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 91956104).

芳香化合物的甲基化反应是一类重要的转化.其中,由芳香卤化物出发的转化是在芳香体系中引入甲基基团的有效策略.已有的方法多需要使用预先制备的甲基金属试剂或高毒性的甲基亲电试剂作为甲基化试剂.本研究发展了一种利用三甲基硅基重氮化合物和芳香溴化物在钯催化下的还原偶联反应生成苄基硅化合物,再经过脱硅质子化过程实现的甲基化方法.此方法具有良好的官能团兼容性,是一种具有潜在应用价值的对芳香卤化物进行甲基化的新方法.同时,该方法也可应用于在有机分子中引入硅甲基基团.

关键词: 甲基化, 三甲基硅基重氮甲烷, 金属卡宾, 转移插入, 还原偶联

The introduction of methyl group into aromatic compounds is a valuable transformation. A large number of known methods use organohalides as the starting materials. However, those methods require pre-synthesized methyl metal reagents or toxic methyl electrophiles. Herein, a palladium-catalyzed reductive coupling reaction between aryl bromides and trimethylsilyl-diazomethane is developed, and the following desilicification process can afford the methylated products. This transformation has broad functional group tolerance and allows methylation of (hetero)aryl halides in moderate to good yields. Thus, it has the potential to be an attractive approach for methylation of organic. In addition, this reductive coupling can also serve as an efficient way for the introduction of silylmethyl group.

Key words: methylation, trimethylsilyldiazomethane, metal carbene, migratory insertion, reductive coupling