Metal-assisted Lossen Rearrangement
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- 作者：Lucie Ja拧铆kov谩 ; Eva Hanik媒艡ov谩 ; Anton 艩kr铆ba ; Juraj Ja拧铆k ; Jana Roithov谩
- 刊名：The Journal of Organic Chemistry
- 出版年：2012
- 出版时间：March 16, 2012
- 年：2012
- 卷：77
- 期：6
- 页码：2829-2836
- 全文大小：456K
- 年卷期：v.77,no.6(March 16, 2012)
- ISSN：1520-6904
文摘
A new reaction mechanism for the Lossen rearrangement of hydroxamic acids catalyzed by basic salts is presented. It is shown that the rearrangement proceeds in metal complexes of deprotonated hydroxamic acids. The deprotonation can occur either at the oxygen atom (observed for the zinc complexes) or at the nitrogen atom (observed for the potassium complexes). Both anionic forms are characterized by infrared multiphoton dissociation spectroscopy. The rearrangements proceed from the reactive N-deprotonated metal hydroxamates and lead to metal carbamates. The mechanism is elucidated by computational chemistry, mass-spectrometric studies, and preparative experiments.