有机化学 ›› 2014, Vol. 34 ›› Issue (5): 916-925.DOI: 10.6023/cjoc201312010 上一篇    下一篇

研究论文

功能化烯胺的合成(Ⅱ):一锅法由缺电子烯烃合成相应的α-脱氢氨

闻化a, 王英杰a, 刘德娥a, 刘亚丽a, 葛淼b, 陈战国a   

  1. a 陕西省大分子科学重点实验室 陕西师范大学化学化工学院 西安 710119;
    b 陕西师范大学旅游与环境学院 西安 710119
  • 收稿日期:2013-12-08 修回日期:2014-01-19 发布日期:2014-02-10
  • 通讯作者: 陈战国 E-mail:chzhg@snnu.edu.cn
  • 基金资助:

    中央高校基本科研业务费专项(No. GK261001095)、陕西省自然科学基金(No. 2009JM2011)、陕西师范大学研究生创新基金(No. 2008CXB009)资助项目.

Synthesis of Functionalized Enamines (Ⅱ):One-Pot Method for the Synthesis of α-Dehydroamino from Electron-Deficient Olefins

Wen Huaa, Wang Yingjiea, Liu Deea, Liu Yalia, Ge Miaob, Chen Zhanguoa   

  1. a Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119;
    b Tourism and Environment College, Shaanxi Normal University, Xi'an 710119
  • Received:2013-12-08 Revised:2014-01-19 Published:2014-02-10
  • Supported by:

    Project supported by the Fundamental Research Funds for the Central Universities (No. GK261001095), the Natural Science Foundation of Shaanxi Province (No. 2009JM2001), and the Innovation Foundation of Postgraduate Cultivation of Shaanxi Normal University (No. 2008CXB009).

建立了一锅法由缺电子烯烃合成相应α-脱氢氨的新方法. 缺电子烯烃(包括αβ-不饱和酯和αβ-不饱和酮)与对甲基苯磺酰胺/NBS在二氯甲烷中,室温下铝粉催化,首先发生双键上的氨溴加成反应,得到邻位氨基溴化合物. 氨溴加成产物不经分离,再在二氯甲烷/DMF(VV=1:1)的混合溶剂中,在碳酸钾/硫脲的催化下,各种邻位氨基溴的酯和邻位氨基溴的酮均能被顺利地转化成相应的α-脱氢氨. 共考察了27种缺电子烯烃的反应行为,最高收率可达97%,证明该方法具有广泛的适应性. 对所有产物的结构分析证明(1H NMR),所得到的脱氢氨,其氨基均处在羰基的α-位,证明该反应具有区域专一性.

关键词: 一锅法, 缺电子烯烃, α-脱氢氨, 合成

An easy and efficient one-pot method for the synthesis of the functionalized enamines from the electron-deficient olefins has been developed. The electron-deficient olefins (including α,β-unsaturated esters and ketones) reacted with p-toluenesulfonamide (TsNH2)/N-bromosuccinimide (NBS) in CH2Cl2 catalyzed by Al powder (5 mol%) at room temperature to generate corresponding α,β-vicinal bromoamines in the first step. Following those, the mixture products without separation can be direct smoothly converted into corresponding α-dehydroamino derivatives catalyzed by thiourea (50 mol%) and K2CO3 (50 mol%) in mixture solvents [V(CH2Cl2):V(DMF)=1:1] at room temperature in good to excellent yields (up to 97%). 27 structurally different electron-deficient substrates were investigated. The results indicate that the protocol has applicability in a large scope of electron-deficient olefins. Based on the analysis of the all products in structure with 1H NMR, it was revealed that the amino groups were linked at the α-position of carbonyl to the dehydroamino derivatives. This result indicates that the one-pot method has full regiospecificity.

Key words: one-pot method, electron-deficient olefins, α-dehydroamino, synthesis