Chinese Journal of Organic Chemistry >
Synthesis of Functionalized Enamines (Ⅱ)：One-Pot Method for the Synthesis of α-Dehydroamino from Electron-Deficient Olefins
Received date: 2013-12-08
Revised date: 2014-01-19
Online 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).
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
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]. Chinese Journal of Organic Chemistry, 2014 , 34(5) : 916 -925 . DOI: 10.6023/cjoc201312010
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