An Efficient and Versatile One-Pot Beckmann Rearrangement of Ketoximes Using Mesitylenesulfonyl Chloride

Abstract

A variety of oxime mesitylenesulfonates, generated in situ from their heterocyclic, carbocyclic, and acyclic ketoximes in the presence of lithium hydroxide in tetrahydrofuran, efficiently rearrange into their corresponding lactams and amides. The stereo­chemistry of diazepan-5-one lactams resulting from the rearrangement of heterocyclic ketoximes (piperidin-4-one oximes), has been deduced based on one- and two-dimensional NMR analyses. The seven-membered heterocyclic ring of the product lactams adopts chair conformations with equatorial configurations of all the alkyl and aryl substituents except one of the methyl groups at C-3 on a 3,3-disubstituted product, which possess an axial configuration.

piperidin-4-one oximes - ketoximes - mesitylenesulfonyl chloride - Beckmann rearrangement - diazepan-5-ones - lactams - amides

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