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.

Key words

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

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11

The E-oxime 1a adopts classical chair-conformation with equatorial orientations of the phenyl groups on C-2 and C-6, and the methyl group on C-3. Key evidence for the orientation of the hydroxyl group of the oxime being anti (E) to C-3 is the unusual downfield absorption of the equatorial proton on C-5 compared to the absorptions of the protons on C-2 and C-6 in the ¹H NMR spectrum, due to the 1,3-spatial proximity effect between the equatorial proton on C-5 and the oxygen of the oxime (Refer to references 10 and 12 for more details).

21

¹H NMR spectra were compared to those obtained from corresponding authentic samples.