Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (7): 1730-1740.DOI: 10.6023/cjoc201704005 Previous Articles     Next Articles

Special Issue: 热点论文合辑

Articles

铜催化的立体选择性Doyle-Kirmse反应

盛哲a,b, 马明b, 彭玲玲b, 张志坤b, 褚长虎a, 张艳b, 王剑波b   

  1. a. 华东理工大学药学院 上海市新药设计重点实验室 上海 200237;
    b. 北京大学化学与分子工程学院 教育部生物有机与分子工程重点实验室 北京 100871
  • 收稿日期:2017-04-05 修回日期:2017-04-23 发布日期:2017-05-04
  • 通讯作者: 褚长虎, 王剑波 E-mail:chuch@ecust.edu.cn;wangjb@pku.edu.cn
  • 基金资助:

    国家自然科学基金(No.21332002)资助项目.

Cu(I)-Catalyzed Stereoselective Doyle-Kirmse Reaction

Sheng Zhea,b, Ma Mingb, Peng Linglingb, Zhang Zhikunb, Chu Changhua, Zhang Yanb, Wang Jianbob   

  1. a. Shanghai Key Laboratory of New Drug Design, School of Pharmacy, East China University of Science and Technology, Shanghai 200237;
    b. Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871
  • Received:2017-04-05 Revised:2017-04-23 Published:2017-05-04
  • Contact: 10.6023/cjoc201704005 E-mail:chuch@ecust.edu.cn;wangjb@pku.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No.21332002).

A highly stereoselective[2,3]-σ rearrangement of sulfur ylide derived from Cu(I) carbene and allyl/propargyl sulfides (Doyle-Kirmse reaction) is reported. High stereocontrol is achieved by a dual asymmetric induction approach which involves a chiral auxiliary on diazo substrate, and steric bulky ligand of the Cu(I) catalyst. From mechanistic study, we suggest the[2,3]-σ rearrangement process occurs through free sulfur ylide intermediate. The reaction was further applied in kinetic resolution of allyl sulfide with a chiral center.

Key words: diazo compounds, carbene, sigmatropic rearrangement, sulfur ylide, asymmetric synthesis, chiral resolution