Chinese Journal of Organic Chemistry >
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).
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
Wang Qiushi , Xie Jianhua , Zhou Qilin . Ruthenium Catalyzed Highly Chemo-and Regio-selective Codimerization of N-Acetyl α-Arylethenamines with Vinylarenes[J]. Chinese Journal of Organic Chemistry, 2019 , 39(8) : 2264 -2269 . DOI: 10.6023/cjoc201903047
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