有机化学 ›› 2001, Vol. 21 ›› Issue (11): 980-985. 上一篇    下一篇

研究论文

α-重氮羰基化合物分解反应的机理以及合成应用

王剑波   

  1. 生物有机与分子工程教育部重点实验室;北京大学化学学院.北京(100871)
  • 发布日期:2001-11-25

Reaction mechanism and synthetic application of α-diazo carbonyl compounds

Wang Jianbo   

  1. Beijing Univ, Coll Chem.Beijing(100871)
  • Published:2001-11-25

本项工作应用物理有机化学的经典方法-Hammett线性自由能相关,对在有机合成中已得到广泛应用的Rh(Ⅱ)-卡宾分子内C-H插入反应的机理进行了深入的探讨。在α-重氮羰基化合物的合成应用方面,发现了Cu(acac)2可以有效地催化α-重氮羰基化合物分解并发生选择的分子内N-H键插入反应。此外,应用α-重氮羰基化合物在Ag(Ⅰ)催化剂的作用下的Wolff重排反应可以有效地合成光学纯的α-内酰胺。

关键词: 羰基化合物, 钌络合物, 铜络合物, 银络合物, 内酰胺P, 重氮化合物, 金属络合物, 卡宾, 插入反应, 分解反应, 反应机理, 合成

In order to gain deep insight into the mechanism of the synthetically well established Rh(Ⅱ)-mediated intramolecular C-H insertion reaction, the classic physical organic chemistry method, the Hammett linear free energy correlation, has been applied. In the development of new synthetic methodologies of α-diazo carbonyl compounds, it was found that Cu(acac)2 can effectively promote the diazo decomposition and resulted in selective intramolecular N-H insertion. On the other hand, the Wolff rearrangement of the α-diazo carbonyl compounds catalyzed by Ag(Ⅰ) has been applied to the efficient synthesis of optically pure α-lactams.

Key words: CARBONYL COMPOUNDS, RUTHENIUM COMPLEX, COPPER COMPLEX, SILVER COMPLEX, LACTAM P, DIAZO COMPOUNDS, METAL COMPLEX, INSERTION REACTION, DECOMPOSITION REACTION, REACTION MECHANISM, SYNTHESIS

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