The Reaction of Ketoximes with Hypervalent Iodine Reagents: Beckmann Rearrangement and Hydrolysis to Ketones

Tomohiro Maegawa*, Ryohei Oishi, Ayumi Maekawa, Kazutoshi Segi, Hiromi Hamamoto, Akira Nakamura, Yasuyoshi Miki*

*School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan, Email: maegawaphar.kindai.ac.jp, y_mikiphar.kindai.ac.jp

T. Maegawa, R. Oishi, A. Maekawa, K. Segi, H. Hamamoto, A. Nakamura, Y. Miki, Synthesis, 2022, 54, 4095-4103.

DOI: 10.1055/a-1835-2188

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Abstract

A combination of PhI(OAc)₂ and BF₃·Et₂O promoted the Beckmann rearrangement of ketoximes to provide amides. The Beckmann rearrangement is preceded by acetylation of the hydroxy group of the ketoxime in situ, accelerating the Beckmann rearrangement. The reaction of ketoximes with Koser's reagent in the presence of THF provides ketones in high yields at room temperature.

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Hypervalent Iodine-Mediated Beckmann Rearrangement of Ketoximes

T. Maegawa, R. Oishi, A. Maekawa, K. Segi, H. Hamamoto, A. Nakamura, Y. Miki, Synthesis, 2022, 54, 4095-4103.

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Key Words

ketoximes, PIDA, Koser's Reagent, Beckmann rearrangement, hydrolysis, amides, ketones

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ID: J66-Y2022