高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (4): 770-776.doi: 10.7503/cjcu20180737

• 物理化学 • 上一篇    下一篇

镍催化氮杂环丁酮和丁二烯环加成反应机制的理论研究

张晓英, 杜桂芳, 朱博, 关威()   

  1. 东北师范大学化学学院, 功能材料化学研究所, 长春 130024
  • 收稿日期:2018-11-01 出版日期:2019-04-03 发布日期:2019-02-25
  • 作者简介:

    联系人简介: 关 威, 男, 博士, 副教授, 博士生导师, 主要从事理论计算化学方面的研究. E-mail: guanw580@nenu. edu. cn

  • 基金资助:
    国家自然科学基金(批准号: 21773025, 21403033)和中央高校基本科研业务费专项资金(批准号: 2412017FZ015)资助.

Theoretical Mechanistic Study on Nickel-Catalyzed Cycloaddition of Azetidinone with Butadiene

ZHANG Xiaoying, DU Guifang, ZHU Bo, GUAN Wei*()   

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2018-11-01 Online:2019-04-03 Published:2019-02-25
  • Contact: GUAN Wei E-mail:guanw580@nenu. edu. cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21773025, 21403033) and the Fundamental Research Funds for the Central Universities, China(No.2412017FZ015).

摘要:

采用密度泛函理论(DFT)方法对镍催化1-Boc-3-氮杂环丁酮和2,3-二甲基-1,3-丁二烯的环加成反应进行了理论研究. 计算结果表明, 该反应采用氧化加成机制而非实验推测的β-碳消除机制. 氧化加成机制主要由3个基元反应步骤组成, 分别为氮杂环丁酮底物中C—C(=O)键的氧化加成、 二烯顺式插入Ni—C(=O)键、 以及还原消除生成八元氮杂环产物, 其中烯烃插入是整个反应的决速步骤, 反应能垒为86.74 kJ/mol. 通过探讨烯烃分别插入到Ni—C(=O) 键和Ni—C(sp3) 键的2种反应途径分析了烯烃插入步骤的区域选择性, 得到了与实验数据基本一致的结果.

关键词: 镍, 环加成反应, 反应机理, 密度泛函理论

Abstract:

Density functional theory(DFT) calculations were carried out on the nickel-catalyzed cycloaddition of 1-Boc-3-azetidinone and 2,3-dimethyl-1,3-butadiene. The calculation results indicate that the reaction occurs via an oxidative addition mechanism rather than experimentally proposed β-carbon elimination mechanism. The important elementary steps consist of the oxidative addition of C—C(=O) bond of azetidinone to Ni(PPh3)2, cis-diene insertion into the Ni—C(=O) bond and the reductive elimination of an eight-membered heterocyclic product. The rate-determining step is the olefin insertion with an acceptable Gibbs activation energy of 86.74 kJ/mol. In addition, the regioselectivity of olefin insertion was investigated. The olefin insertion into Ni—C(=O) bond is more favorable than that into Ni—C(sp3) bond, which agrees well with the experimental observation.

Key words: Nickel, Cycloaddition reaction, Reaction mechanism, Density functional theory

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