有机化学 ›› 2012, Vol. 32 ›› Issue (01): 160-164.DOI: 10.6023/cjoc1106191 上一篇    下一篇

研究简报

Evans 手性助剂控制的不对称Michael 加成立体选择性研究(Ⅱ)

樊会丹, 张从海, 严胜骄, 林军   

  1. 云南大学化学科学与工程学院 教育部自然资源药物化学重点实验室 昆明 650091
  • 收稿日期:2011-06-19 修回日期:2011-08-02 发布日期:2011-09-26
  • 通讯作者: 林军 E-mail:linjun@ynu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 30860342, 20762013)和云南省自然科学基金(No. 2009CC017)资助项目.

Asymmetric Michael Addition Reaction under the Control of the Evans Chiral Auxiliary (Ⅱ)

Fan Huidan, Zhang Conghai, Yan Shengjiao, Lin Jun   

  1. Key Laboratory of Medicinal Chemistry for Natural Resources, Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming 650091
  • Received:2011-06-19 Revised:2011-08-02 Published:2011-09-26
  • Contact: Lin Jun E-mail:linjun@ynu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 30860342, 20762013) and the Natural Science Foundation of Yunnan Province (No. 2009CC017).

手性助剂控制的不对称反应是不对称合成的重要方法之一. 以Evans 手性助剂控制的Michael 受体1 为底物, 在FeCl3 催化下, 通过不同格式试剂对其进行Michael 加成, 一步反应得到了一系列含两个手性中心的Michael 加成产物2a2h. 获得了较高的立体选择性, 其中化合物2d2e 得到了de 值高达98%的非对映选择性. 研究结果表明, 亲核试剂的空间位阻是影响产物立体选择性的主要因素.

关键词: 不对称Michael 加成, Evans 手性助剂, 非对映选择性

Chiral auxiliaries controlled asymmetric reaction is one of the main methods in asymmetric synthesis. Under the control of the Evans auxiliary and catalyzed by FeCl3, different Grignard reagents were added asymmetrically to the substrates 1 by the way of 1,4-Michael addition reaction, and a series of Michael addition products 2a2h which containing two chiral centers have been synthesized with higher stereoselectivity. Among them, compounds 2d and 2e achieved high diastereospecifically up to 98% de. The results showed that the steric hindrance of the Grignard reagents is the main factor which influences the stereoselectivity of Micheal addition.

Key words: asymmetric Michael addition, Evans chiral auxiliary, diastereoselectivity