有机化学 ›› 2016, Vol. 36 ›› Issue (4): 752-759.DOI: 10.6023/cjoc201602032 上一篇    下一篇

研究论文

手性磷酸控制的不对称碳氢芳基化反应合成平面手性二茂铁化合物

张松a, 陆俊筑a, 叶金星a, 段伟良b   

  1. a. 华东理工大学药学院 制药工程与过程化学研究中心 上海 200237;
    b. 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032
  • 收稿日期:2016-02-28 修回日期:2016-03-30 出版日期:2016-04-25 发布日期:2016-04-05
  • 通讯作者: 叶金星, 段伟良 E-mail:wlduan@mail.sioc.ac.cn;yejx@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.20902099,21172238,21472218)资助项目.

Asymmetric C-H Arylation for the Synthesis of Planar Chiral Ferrocenes: Controlling Enantioselectivity Using Chiral Phosphoric Acids

Zhang Songa, Lu Junzhua, Ye Jinxinga, Duan Wei-liangb   

  1. a. School of Pharmacy, East China. University of Science and Technology, Shanghai 200237;
    b. State Key Laboratory of Organometallic. Chemistry, Shanghai Institute of Organic. Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2016-02-28 Revised:2016-03-30 Online:2016-04-25 Published:2016-04-05
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 20902099, 21172238, 21472218).

报道了钯催化的分子内不对称C-H键芳基化反应.以简单易得的二茂铁羰基化合物为底物,Pd(CH3CN)4(OTf)2为催化剂,使用手性磷酸作为唯一手性源,Buchwald类型联苯单膦配体,甲苯作溶剂,100℃进行反应,得到一系列二茂铁化合物,ee值最高可达83%.该反应为合成平面手性二茂铁化合物提供了一种新途径.

关键词: 钯催化, C-H键活化, 不对称催化, 手性磷酸, 二茂铁

Transition-metal-catalyzed direct activation reactions of unreactive C-H bond has been extensively developed in recent years. Although numerous synthetic methods have been reported to build diverse complex compounds, enantioselective C-H activation has not been paid much attention probably because of the absence of suitable ligands to control the stereoselectivity in the C-H activation reaction. Herein, a Pd(0)-catalyzed enantioselective synthesis of planar chiral ferrocenes was described, and chiral phosphoric acids were used as the only chiral source to control the stereoselectivity in the C-H activation reactions.

Key words: palladium catalysis, C-H activation, asymmetric catalysis, chiral phosphoric acids, ferrocenes