有机化学 ›› 2019, Vol. 39 ›› Issue (8): 2264-2269.DOI: 10.6023/cjoc201903047 上一篇    下一篇

所属专题: 陈茹玉先生诞辰100周年

研究论文

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).

过渡金属催化的烯烃的二聚反应是碳-碳键形成的重要反应之一.因其原料易得、原子经济、且具有很好的工业应用前景而已得到深入、广泛的研究.系统研究了钌催化N-乙酰基烯胺与烯烃的二聚反应,发现在钌氢络合物RuHCl(CO)(PCy32的催化下可实现系列N-乙酰基α-芳基乙烯胺1与芳基乙烯4的高化学选择性和区域选择性二聚,并以高达99%的收率得到头对尾的多取代烯酰胺5.依据反应结果及反应中观测到的现象,提出了芳基乙烯4先与活化的钌氢中间体发生插入反应形成类烯丙基中间体,然后与N-乙酰基α-芳基乙烯胺1发生二聚反应生成多取代烯酰胺5的可能机理,并对反应中观测到的现象进行了合理的解释.

关键词: 二聚, 碳-碳键形成, 烯酰胺, 钌, 芳基乙烯

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