Acta Scientiarum Naturalium Universitatis Pekinensis

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The Reaction Mechanism and Synthetic Application of α-Diazo Carbonyl Compounds

JIANG Nan,WANG Lin,WANG Jianbo   

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871
  • Received:2000-05-22 Online:2001-07-20 Published:2001-07-20



  1. 北京大学化学与分子工程学院,北京,100871

Abstract: α-Diazo carbonyl compounds can be decomposed under various conditions and result in diverse types of chemical transformations. For this reason, their application in organic synthesis have attracted considerable attention. 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 γ-lactams.

Key words: synthesis, reaction mechanism, metal-carbene, C-H insertion, metal-carbene, C-H insertion, synthesis, reaction mechanism

摘要: α-重氮羰基化合物在不同条件下的分解反应,在有机合成中有多种多样的应用,因此引起人们的广泛关注。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性的分子内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γ-内酰胺。

关键词: 合成, 反应机理, 金属卡宾, C-H插入反应, 金属卡宾, C-H插入反应, 合成, 反应机理

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