Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (1): 107-111.DOI: 10.6023/cjoc201310053 Previous Articles     Next Articles


倪懿, 郭鑫, 胡文浩, 刘顺英   

  1. 华东师范大学上海市分子治疗与新药创制工程技术研究中心 上海 200062
  • 收稿日期:2013-10-31 修回日期:2013-11-25 发布日期:2013-11-28
  • 通讯作者: 刘顺英, Tel./Fax: 86-21-62221237
  • 基金资助:

    国家杰出青年科学基金(No. 21125209);上海市科委重点基础研究基金(No. 12JC1403800)及上海市闵行区高层次选拔人才计划资助项目.

Asymmetric N—H Insertion Reaction of α-Diazoesters and Carbamates Co-catalyzed by Dirhodium Acetate, Sufonic Acid and Chiral Sulfonamide Urea

Ni Yi, Guo Xin, Hu Wenhao, Liu Shunying   

  1. Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, Shanghai 200062
  • Received:2013-10-31 Revised:2013-11-25 Published:2013-11-28
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21125209), the Science and Technology Commission of Shanghai Municipality (No. 12JC1403800) and the Minhang District Government in Shanghai.

The enantioselective N—H insertion of α-diazoesters and carbamates provides a potentially attractive approach to α-amino acid derivatives. Herein, a novel cooperative catalytic system of achiral dirhodium(Ⅱ) acetates, chiral sulfonamide urea and achiral sulfonic acid was developed for asymmetric N—H insertion reactions. Prochiral ammonium ylide intermediates, generated in situ from α-diazoesters and carbamates initiated by dirhodium(Ⅱ) acetate, underwent asymmetric protonation with a considerable enantioselectivity in the presence of chiral sulfonamide urea and achiral sulfonic acid as co-catalysts. The co-catalysts of chiral sulfonamide urea and achiral sulfonic acid were considered as a chiral proton shuttle assisting the asymmetric proton transfer process to control the enantioselectivity. This methodology provides an efficient and mild approach to α-amino acid derivatives in high yields (up to 84% yield) with moderate enantioselectivity (up to 77% ee).

Key words: N—H insertion, chiral sulfonamide urea, ammonium ylide, co-catalysts, α-amino acid derivatives