Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (9): 1093-1100. Previous Articles     Next Articles

Full Papers

铝粉催化肉桂酸酯衍生物区域选择和立体选择性氨溴加成反应研究

陈战国*,周利燕,李文丽,周继梅,王传宁   

  1. (陕西师范大学化学与材料科学学院 陕西省大分子科学重点实验室 西安 710062)
  • 投稿日期:2010-10-28 修回日期:2010-12-03 发布日期:2011-01-07
  • 通讯作者: 陈战国 E-mail:chzhg@snnu.edu.cn
  • 基金资助:

    烯键上选择性氨卤双官能化反应的新方法研究;烯键上的氨卤加成反应新体系研究(陕西师范大学研究生创新基金)

Aluminium Powder-catalyzed Regio- and Stereoselective Aminobromination of Cinnamic Ester Derivatives

CHEN Zhan-Guo, ZHOU Li-Yan, LI Wen-Li, ZHOU Ji-Mei, WANG Chuan-Ning   

  1. (School of Chemistry and Materials Science, Shaanxi Normal University, Key Laboratory of Macromolecular Science of Shaanxi Province, Xi an 710062)
  • Received:2010-10-28 Revised:2010-12-03 Published:2011-01-07
  • Contact: Chen Zhan-guo E-mail:chzhg@snnu.edu.cn

A new system for the high regio- and stereoselective aminohalogenation of cinnamic esters with NBS and p-toluenesulfonamide (TsNH2) as bromine/nitrogen sources catalyzed by Al powder in CH2Cl2 has been developed. This method offered vicinal haloamine products in high yield (up to 97%) at room temperature without inert gases protection. The cinnamic esters bearing a strong electron-donating group (e.g., OCH3) on the 4-position of the benzene ring afforded the trans isomer as the sole products of α-bromine and β-amine adductive products up to nearly quantitative yields. However, the cinnamic esters without the strong electron-donating group (e.g., OCH3) or bearing a poor electron-withdrawing group (Br) on the 4-position of the benzene ring, the yield of reaction was decreased and the α-amine and β-bromine adductive products as sole product were afforded. These results of experiment indicated that the aminohalogenation to cinnamic esters catalyzed by Al-powder is an electrophilic addition reaction. In this paper, a series of the aminohalogenation of cinnamic esters (20 samples) has been investigated. All products structure were characterized by elemental analysis, 1H NMR and 13C NMR and the possible reaction pathway have been proposed.

Key words: aminobromination, Al powder, cinnamic ester derivatives, regioselective, stereoselective