物理化学学报 >> 2012, Vol. 28 >> Issue (03): 561-566.doi: 10.3866/PKU.WHXB201201112

理论与计算化学 上一篇    下一篇

硫脲催化硝基烯与硫叶立德的不对称Michael加成反应

孙香婷, 张冬菊, 冯大诚, 刘成卜   

  1. 山东大学化学与化工学院, 理论化学研究所, 济南 250100
  • 收稿日期:2011-12-05 修回日期:2012-01-04 发布日期:2012-02-23
  • 通讯作者: 张冬菊 E-mail:zhangdj@sdu.edu.cn
  • 基金资助:

    国家自然科学基金(20873076)和教育部博士点基金(200804220009)资助项目

Asymmetric Michael Addition between Nitroolefins and Sulfur Ylides Catalyzed by a Thiourea Organocatalyst

SUN Xiang-Ting, ZHANG Dong-Ju, FENG Da-Cheng, LIU Cheng-Bu   

  1. School of Chemistry and Chemical Engineering, Institute of Theoretical Chemistry, Shandong University, Jinan 250100, P. R. China
  • Received:2011-12-05 Revised:2012-01-04 Published:2012-02-23
  • Contact: ZHANG Dong-Ju E-mail:zhangdj@sdu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20873076) and Specialized Research Fund for the Doctoral Program of Higher Education, China (200804220009).

摘要: 基于密度泛函理论研究了氯代苯基硫脲催化的硝基苯乙烯与硫叶立德的Michael 加成反应, 确定了控制反应立体选择性的C―C键形成步骤的过渡态结构, 计算了过渡态的相对能量和反应势垒, 弄清了硫脲催化的微观反应机理, 探讨了硫脲催化性能的微观本质. 结果表明, 反应有利于反式Michael 加成产物的形成, 硫脲在反应中作为质子给体, 首先与质子受体硝基苯乙烯形成双氢键配合物, 通过授受体间的电荷转移活化硝基苯乙烯的β-C原子增强其亲电性, 有利于硫叶立德的亲核进攻.

关键词: 硫脲, 硝基苯乙烯, 硫叶立德, 不对称Michael 加成, 密度泛函理论

Abstract: Using density functional theory calculations, we have studied the 1-(2-chlorophenyl)-2-thiourea catalyzed reaction of nitrostyrene with a typical sulfur ylide to understand the Michael addition mechanism. Transition state structures for the C―C bond-forming step controlling the stereoselectivity of the reaction have been identified and their relative stabilities evaluated. The role of the catalyst in the reaction has also been determined. The calculated results show that the formation of the anti-product is energetically more favorable than that of the syn-product. Furthermore, the catalyst (proton donor) promotes the reaction by forming a double hydrogen-bonded complex with nitrostyrene (proton acceptor), where the charge transfer between the donor and acceptor increases the eletrophilicity of β-C atom of the nitrostyrene, favoring the nucleophilic attack of the sulfur ylide.

Key words: Thiourea, Nitroolefin, Sulfur ylide, Asymmetric Michael addition, Density functional theory

MSC2000: 

  • O641