Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (1): 117-121.DOI: 10.6023/cjoc201809026 Previous Articles     Next Articles

Special Issue: 庆祝陈庆云院士九十华诞

Articles

含氟咪唑啉型有机催化剂在不对称Aldol反应中的研究

解晓娟a, 张忠a, 赵华欣a, 万文a,b, 郝健a,b   

  1. a 上海大学化学系 上海 200444;
    b 中国科学院上海有机化学研究所 有机氟化学重点实验室 上海 200032
  • 收稿日期:2018-09-21 修回日期:2018-12-05 出版日期:2019-01-25 发布日期:2018-12-07
  • 通讯作者: 万文, 郝健 E-mail:wanwen@shu.edu.cn;jhao@shu.edu.cn
  • 基金资助:

    国家自然科学基金基(Nos.21572128,21672139)及中国科学院上海有机化学研究所氟重点实验室开放基金资助项目.

Trifluoromethylated-Imidazolines as Efficient Organocatalyst for Asymmetric Aldol Reaction of Hydroxyacetone with Aldehydes

Xie Xiaojuana, Zhang Zhonga, Zhao Huaxina, Wan Wena,b, Hao Jiana,b   

  1. a Department of Chemistry, Shanghai University, Shanghai 200444;
    b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2018-09-21 Revised:2018-12-05 Online:2019-01-25 Published:2018-12-07
  • Contact: 10.6023/cjoc201809026 E-mail:wanwen@shu.edu.cn;jhao@shu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21572128, 21672139) and the Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science.

Aldol reaction of hydroxyacetone is an all-purpose route to construct the 1,2-diol building blocks for the synthesis of multifarious natural products and biological active molecules. In this work, a new series of trifluoromethylated-imidazoline organocatalysts have been designed and synthesized. It is found that the trifluoromethylated chiral organocatalyst (2R,4S)-4-benzyl-1,2-dimethyl-2-(trifluoromethyl) imidazolidine (1a) has proved to be very efficient for the direct asymmetric aldol reaction of α-hydroxyketones with aldehydes to build the syn-1,2-diol building blocks. Among the synthesized syn-aldol products, a good yield (up to 96%) and high stereoselectivity (up to dr=15:1, 99% ee) could be obtained. The F—H bonding derived from trifluoromethyl group was proposed to play an important role in the stabilization of the transition state.

Key words: asymmetric aldol reaction, organocatalysis, imidazoline, trifluoromethyl, synthesis