文献类型：期刊文献

英文题名：Mechanistic Insight into Self-Propagation of Organo-Mediated Beckmann Rearrangement: A Combined Experimental and Computational Study

作者：An, Na[1,2];Tian, Bo-Xue[3];Pi, Hong-Jun[1,2];Eriksson, Leif A.[4];Deng, Wei-Ping[1,2]

机构：[1]E China Univ Sci & Technol, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China;[3]Natl Univ Ireland Galway, Sch Chem, Galway, Ireland;[4]Univ Gothenburg, Dept Chem & Mol Biol, S-41296 Gothenburg, Sweden

年份：2013

卷号：78

期号：9

起止页码：4297

外文期刊名：JOURNAL OF ORGANIC CHEMISTRY

收录：;EI(收录号：20131916321464);WOS:【SCI-EXPANDED(收录号:WOS:000318588800010)】；

基金：The National Natural Science Foundation of China (No. 20602011, 20972047), the Fundamental Research Funds for the Central Universities, the Shanghai Committee of Science and Technology (No. 11DZ2260600), the National University of Ireland-Galway, and the Faculty of Science of the University of Gothenburg are gratefully acknowledged for financial support.

语种：英文

摘要：Organo-mediated Beckmann rearrangement in the liquid phase, which has the advantage of high efficiency and straightforward experimental procedures, plays an important role in e synthesis of amides from oximes. However, the catalytic mechanisms of these organic-based promoters are still not well understood. In this work, we report a combined experimental and computational study on the mechanism of Beckmann rearrangement mediated by Organic-based promoters, using TsCl as an example. A novel self-propagating cycle is proposed, and key intermediates of this self-propagating cycle are confirmed by both experiments and DFT calculations. In addition, the reason why cyclohexanone oxime is not a good substrate of the organo-mediated Beckmann rearrangement is discussed, and a strategy for improving the yield is proposed.