Wolff重排
α-重氮酮重排得到烯酮的反应。烯酮是非常重要的有机中间体。可以和水反应制备羧酸,和醇反应制备酯,和胺反应制备酰胺,发生Staudinger烯酮环加成合成各种四元环化合物(可以和烯烃,醛酮和亚胺进行 [2 + 2] 环加成得到环丁酮,β -内酯和β -内酰胺)。
反应机理
可能的有两种机理,一种是先裂解生卡宾,再重排:

另一种是整个过程协同进行:

反应实例




参考文献
1. Wolff, L. Ann. 1912, 394, 23-108. Johann Ludwig Wolff (1857-1919) earned his doctorate in 1882 under Fittig at Strasbourg, where he later became an instructor. In 1891, Wolff joined the faculty of Jena, where he collaborated with Knorr for 27 years.
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2193-2256. (Review).
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10. Kumar, R. R.; Balasubramanian, M. Wolff Rearrangement. In Name Reactions for Homologations-Part II; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 257-273. (Review).
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Johann Ludwig Wolff (1857-1919),1882年在斯特拉斯堡大学的Fittig处获得博士学位,并在那里出任讲师。1891年进入耶拿大学任教,在那里他和Knorr合作了27年。
编译自:J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Wolff rearrangement,page 642-643.
