有机化学 ›› 2016, Vol. 36 ›› Issue (10): 2397-2406.DOI: 10.6023/cjoc201606039 上一篇    下一篇

研究论文

An-PIQ催化的β-碘代Morita-Baylis-Hillman加合物动力学拆分研究

朱明玉, 邓卫平   

  1. 华东理工大学药学院 上海市功能性材料化学重点实验室 上海 200237
  • 收稿日期:2016-06-26 修回日期:2016-07-24 发布日期:2016-08-25
  • 通讯作者: 邓卫平,E-mail:weiping_deng@ecust.edu.cn E-mail:weiping_deng@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(No.21372074)资助项目.

An-PIQ Catalyzed Kinetic Resolution of β-Iodo Morita-Baylis-Hillman Adducts

Zhu Mingyu, Deng Weiping   

  1. Shanghai Key Laboratory of Functional Materials Chemistry & School of Pharmacy, East China University of Science and Technology, Shanghai 200237
  • Received:2016-06-26 Revised:2016-07-24 Published:2016-08-25
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No.21372074).

β-碘代Morita-Baylis-Hillman(MBH)加合物作为一种多官能团的手性砌块,是多种天然产物和药物分子的重要中间体.以课题组最近开发的An-PIQ为亲核催化剂,首次利用非酶亲核酰化动力学拆分的方法获得了一系列高光学纯β-碘代MBH加合物,S值最高可达165.该方法不仅解决了脂肪醛衍生的MBH加合物二级醇在动力学拆分中的低选择性问题,而且具有条件温和,较好的底物普适性,并能放大到克级规模等特点.

关键词: β-碘代MBH加合物, 亲核催化, 对映选择性, 动力学拆分

Chiral β-iodo Morita-Baylis-Hillman (MBH) adducts are important versatile synthetic building blocks for many nat-ural products and drug molecules. By using a recently developed acyl transfer catalyst An-PIQ, the kinetic resolutions of a series of β-iodo MBH adducts were investigated, providing the recovered alcohols in good yields with high enantioselectivities (up to 99.9% ee) and good selectivity factors (S up to 165). This method overcomes the issue of low selectivity confronted in the kinetic resolution of aliphatic aldehyde-derived MBH adducts as secondly alcohols, and features mild reaction conditions, broad sub-strate scope, and easy scaling-up to gram scale.

Key words: β-iodo MBH adducts, nucleophilic catalysis, enantioselectivity, kinetic resolution