有机化学 ›› 2014, Vol. 34 ›› Issue (1): 107-111.DOI: 10.6023/cjoc201310053 上一篇    下一篇

研究论文

基于醋酸铑、磺酸和手性亚磺酰胺基脲共催化的α-重氮酯与酰胺不对称N—H插入反应研究

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 出版日期:2014-01-25 发布日期:2013-11-28
  • 通讯作者: 刘顺英 E-mail:syliu@sist.ecnu.edu.cn, 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 Online:2014-01-25 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.

研究了醋酸铑[Rh2(OAc)4]、手性亚磺酰胺基脲和非手性磺酸共催化的α-重氮酯与酰胺化合物的不对称N—H插入反应. 研究发现α-重氮酯在醋酸铑催化下形成金属卡宾,该金属卡宾与酰胺反应生成潜手性活泼叶立德中间体. 在催化剂量的手性亚磺酰胺基脲和非手性磺酸存在下,潜手性叶立德中间体发生不对称质子化,合成了手性α-氨基酸衍生物. 反应过程中,手性亚磺酰胺基脲和非手性磺酸作为“手性质子梭”催化不对称质子迁移从而实现了反应的对映选择性控制. 该方法发展了非手性铑、手性亚磺酰胺基脲和非手性磺酸不对称共催化体系,为合成α-氨基酸衍生物提供了一种新途径,反应收率最高可达84%,对映选择性最高可达77%.

关键词: N—H插入, 手性亚磺酰胺基脲, 铵基叶立德, 共催化, α-氨基酸衍生物

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