催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (6): 899-903.DOI: 10.1016/S1872-2067(10)60237-9

• 研究论文 • 上一篇    下一篇

手性伯胺催化剂用于顺式选择性的不对称 Cross-Aldol 反应

高强 1,2, 刘1, 卢胜梅 1, 李灿 1,*   

  1. 1 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023; 2 中国科学院研究生院, 北京 100049
  • 收稿日期:2011-03-29 修回日期:2011-04-21 出版日期:2011-06-21 发布日期:2014-10-31

Chiral Primary Amine Organocatalysts for Syn-selective Asymmetric Cross-Aldol Reactions

GAO Qiang1,2, LIU Yan1, LU Shengmei1, LI Can1,*   

  1. 1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China; 2Graduate University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2011-03-29 Revised:2011-04-21 Online:2011-06-21 Published:2014-10-31

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1590

被引次数

2

摘要： 基于酸碱作用, 将手性伯胺与质子酸原位结合制得有机小分子催化剂, 并用于醛与醛的不对称 Cross-aldol 反应. 与一般手性仲胺催化剂不同, 该类伯胺催化剂得到的是顺式选择性构型的 Cross-aldol 产物, 其产率达 90%, 顺反比和 ee 值分别为 9:1 和 90%. 相比而言, 采用简单易得的 (1S,2S)-(+)-环己二胺即可得到较高选择性的顺式产物.

关键词: 手性伯胺, 有机催化, 不对称催化, Cross-aldol 反应

Abstract: Based on the “acid-base” interaction strategy, organocatalysts for the asymmetric cross-aldol reaction were synthesized by the in situ combination of chiral primary amines with protonic acids. Unlike general secondary amine catalysts that give anti-selective products, as-prepared primary amine catalysts can give syn-selective cross-aldol products with high yield and high selectivity (up to 90% yield, 90:10 syn/anti ratio, 90% ee). Compared with the complex synthesis of the reported catalysts, the primary amine catalyst that gave the best results was easily prepared using commercial available (1S,2S)-(+)-cyclohexanediamine.

Key words: chiral primary amine, organocatalysis, asymmetric catalysis, cross-aldol reaction