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

doi:10.6023/cjoc201312010

Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (5): 916-925.DOI: 10.6023/cjoc201312010 Previous Articles Next Articles

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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

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 Hua^a, Wang Yingjie^a, Liu Dee^a, Liu Yali^a, Ge Miao^b, Chen Zhanguo^a

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).

1. Synthesis of Functionalized Enamines (Ⅱ)：One-Pot Method for the Synthesis of α-Dehydroamino from Electron-Deficient Olefins.PDF(1124KB)

Abstract

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

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Wen Hua, Wang Yingjie, Liu Dee, Liu Yali, Ge Miao, Chen Zhanguo. Synthesis of Functionalized Enamines (Ⅱ)：One-Pot Method for the Synthesis of α-Dehydroamino from Electron-Deficient Olefins[J]. Chin. J. Org. Chem., 2014, 34(5): 916-925.

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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

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

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