有机化学 ›› 2014, Vol. 34 ›› Issue (11): 2187-2194.DOI: 10.6023/cjoc201406038 上一篇    下一篇

特邀研究专题

Lewis碱催化的α-胺基腈及氰醇的烯丙基官能团化反应研究及应用

秦天游a,b, 张晓安a,b, 寮渭巍b   

  1. a 大连理工大学精细化工国家重点实验室 大连 116024;
    b 吉林大学化学学院 长春 130012
  • 收稿日期:2014-06-23 修回日期:2014-08-03 出版日期:2014-11-25 发布日期:2014-08-11
  • 通讯作者: 寮渭巍,wliao@jlu.edu.cn E-mail:wliao@jlu.edu.cn
  • 基金资助:

    国家自然科学基金(No.21372096)资助项目.

Lewis Base-Catalyzed Allylic Alkylation of α-Amino Nitriles and Cyanohydrins and Synthetic Applications

Qin Tianyoua,b, Zhang Sean Xiao-Ana,b, Liao Weiweib   

  1. a State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024;
    b Department of Organic Chemistry, College of Chemistry, Jilin University, Changchun 130012
  • Received:2014-06-23 Revised:2014-08-03 Online:2014-11-25 Published:2014-08-11
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No.21372096).

对我们研究小组近几年在Lewis碱催化具有α-位氢的α-胺基腈类及氰醇类化合物与Morita-Baylis-Hillman (MBH)加合物立体选择性的烯丙基化反应方面取得的初步成果进行了小结. 通过与MBH加合物的烯丙基取代反应, 有效地构建了具有α-位季碳结构单元的多官能团腈类衍生物, 而且基于此发展了一类非金属催化的烯烃分子内氰官能团化反应, 构建了β-位有季碳结构单元的官能团化的腈类化合物. 此外对影响反应的可能因素也做了讨论, 提出了可能的反应机理.

关键词: 烯丙基化, 路易斯碱, 催化, α-胺基腈, 氰醇, 碳氰化反应

This article summarized our recent progress in Lewis base-catalyzed the direct allylic substitutions of Morita-Baylis-Hillman (MBH) adducts with α-amino nitriles and cyanohydrins bearing an α-hydrogen, which provided efficient access to functionalized α-amino nitriles and cyanohydrins incorporating quaternary carbon centers. On the basis of these, a novel metal-free carbocyanation (alkenylcyanation and acylcyanation) approach to construct functionalized nitriles incorporating β-quaternary carbon center has been developed. In addition, the several factors influencing these chemical transformations are discussed, and the possible mechanism is proposed.

Key words: allylic alkylation, Lewis base, catalysis, α-amino nitriles, cyanohydrins, carbocyanation