Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (8): 2264-2269.DOI: 10.6023/cjoc201903047 Previous Articles     Next Articles

Special Issue: 陈茹玉先生诞辰100周年

Articles

钌催化N-乙酰基α-芳基乙烯胺与芳基乙烯的高化学选择性和区域选择性二聚

王秋实, 谢建华, 周其林   

  1. 南开大学化学学院 元素有机化学国家重点实验室 天津 300071
  • 收稿日期:2019-03-23 修回日期:2019-04-22 出版日期:2019-08-25 发布日期:2019-05-10
  • 通讯作者: 谢建华, 周其林 E-mail:jhxie@nankai.edu.cn;qlzhou@nankai.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21532003,21871152,21790332)和教育部“111”引智计划(No.B06005)资助项目.

Ruthenium Catalyzed Highly Chemo-and Regio-selective Codimerization of N-Acetyl α-Arylethenamines with Vinylarenes

Wang Qiushi, Xie Jianhua, Zhou Qilin   

  1. State Key Laboratory and Institute of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071
  • Received:2019-03-23 Revised:2019-04-22 Online:2019-08-25 Published:2019-05-10
  • Contact: 10.6023/cjoc201903047 E-mail:jhxie@nankai.edu.cn;qlzhou@nankai.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21532003, 21871152, 21790332) and the "111" Project of the Ministry of Education of China (No. B06005).

Transition metal catalyzed codimeriaztion of alkenes is an important carbon-carbon bond forming reaction. This efficient reaction has the properties of easily available of starting materials, atomic economy, and good prospects for industrial application, and has been received in-depth and intensive study during the past decades. In this paper, we have systematically studied the ruthenium catalyzed codimerization of N-acetyl enamides with alkenes and found that the ruthenium hydride complex RuHCl(CO)(PCy3)2 is highly efficient catalyst for the codimerization of N-acetyl α-arylethenamines 1 with vinylarenes 4, providing the head-to-tail hetero-codimerized products, poly-substituted N-acetyl enamides 5 with high chemo-and regio-selectivity and up to 99% yield. According to the results and the observed phenomena of the codimerization reaction, we proposed a reaction mechanism that the vinylarenes 4 was firstly inserted into the Ru-H bond of the activated ruthenium hydride intermediate to form an allylic metal-intermediate and then codimerized with N-acetyl α-arylethenamines 1 to generate the hetero-codimerized poly-substituted N-acetyl enamides 5. With this proposed reaction mechanism the reaction results and the observed phenomena can be rational explanation.

Key words: codemerization, carbon-carbon bond forming, enamides, ruthenium, vinylarenes