有机化学 ›› 2020, Vol. 40 ›› Issue (3): 651-662.DOI: 10.6023/cjoc201911016 上一篇    下一篇

所属专题: 镍催化有机反应虚拟合辑

研究论文

镍催化环丁酮肟酯与芳基锌试剂的Negishi偶联反应

帅斌, 李兆明, 裘晖, 方萍, 梅天胜   

  1. 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 分子合成科学卓越中心中国科学院大学 上海 200032
  • 收稿日期:2019-11-08 修回日期:2019-12-11 发布日期:2019-12-19
  • 通讯作者: 方萍, 梅天胜 E-mail:mei7900@sioc.ac.cn;pfang@sioc.ac.cn
  • 基金资助:
    中国科学院战略性先导科技专项(No.XDB20000000)、国家自然科学基金(Nos.21572245,21772222,21772220)、上海市科委(Nos.17JC1401200,18JC1415600)资助项目.

Nickel-Catalyzed Negishi Coupling of Cyclobutanone Oxime Esters with Aryl Zinc Reagents

Shuai Bin, Li Zhao-Ming, Qiu Hui, Fang Ping, Mei Tian-Sheng   

  1. State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032
  • Received:2019-11-08 Revised:2019-12-11 Published:2019-12-19
  • Supported by:
    Project supported by the Strategic Priority Research Program (No. XDB20000000), the National Natural Science Foundation of China (Nos. 21572245, 21772222, 21772220), and the Shanghai Committee of Science and Technology (Nos. 17JC1401200, 18JC1415600).

发展了一种镍催化环丁酮肟酯和芳基锌试剂之间Negishi偶联的方法.镍既作为亚胺自由基的引发剂,也作为芳基锌试剂与烷基自由基偶联反应的催化剂在反应中起作用.本方法可避免使用剧毒的氰化物,且具有很广的底物适应性和官能团兼容性,因此可能是一种具有潜在吸引力的高效合成烷基腈类化合物的新策略.初步的机理研究显示,该反应极可能经历自由基历程.

关键词: Negishi偶联, 镍, 环丁酮肟酯, 芳基锌试剂

A nickel-catalyzed Negishi coupling of cyclobutanone oxime esters with aryl zinc reagents has been developed, in which nickel serves both as an initiator for imine radicals and a catalyst for the coupling of aryl zinc reagents with oxime esters. The protocol can avoid the use of poisonous cyanide and has broad substrate scope as well as good functional group compatibility. Therefore, this method provides an attractive strategy for the synthesis of valuable nitriles. Preliminary mechanistic studies indicate that a radical pathway is involved in the product formation.

Key words: Negishi coupling, nickel, cyclobutanone oxime esters, aryl zinc reagents