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
收稿日期: 2019-03-23
修回日期: 2019-04-22
网络出版日期: 2019-05-10
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
Received date: 2019-03-23
Revised date: 2019-04-22
Online published: 2019-05-10
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）（PCy3）2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.
王秋实 , 谢建华 , 周其林 . 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[J]. 有机化学, 2019 , 39(8) : 2264 -2269 . DOI: 10.6023/cjoc201903047
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
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