DOIAbstract
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α-内酰胺.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 alpha-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 alpha-diazo carbonyl compound...
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