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J Org Chem. 2013 May 3;78(9):4297-302. doi: 10.1021/jo400278c. Epub 2013 Apr 10.

Mechanistic insight into self-propagation of organo-mediated Beckmann rearrangement: a combined experimental and computational study.

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Shanghai Key Laboratory of New Drug Design & School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China.


Organo-mediated Beckmann rearrangement in the liquid phase, which has the advantage of high efficiency and straightforward experimental procedures, plays an important role in the 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.

[Indexed for MEDLINE]

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