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

doi:10.1055/a-1835-2188

Synthesis, Table of Contents

Synthesis 2022; 54(18): 4095-4103
DOI: 10.1055/a-1835-2188

paper

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

Authors

Tomohiro Maegawa ∗

^aSchool of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
Ryohei Oishi

^aSchool of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
Ayumi Maekawa

^aSchool of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
Kazutoshi Segi

^aSchool of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan
Hiromi Hamamoto

^bFaculty of Agriculture, Meijo University, 1-501 Shiogamaguchi, Tempaku, Nagoya, 468-8502, Japan
Akira Nakamura

^aSchool of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan

^cResearch Organization of Science and Technology, Research Center for Drug Discovery and Pharmaceutical Science, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu, Shiga, 525-8577, Japan
Yasuyoshi Miki∗

^aSchool of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan

^cResearch Organization of Science and Technology, Research Center for Drug Discovery and Pharmaceutical Science, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu, Shiga, 525-8577, Japan

Abstract

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Abstract

We investigated the reaction of ketoximes with hypervalent iodine reagents. A combination of PhI(OAc)₂ and BF₃·Et₂O promoted the Beckmann rearrangement of ketoximes, thus yielding the corresponding amides. From a detailed investigation of the reaction, we determined that the Beckmann rearrangement is preceded by acetylation of the hydroxy group of the ketoxime in situ, accelerating the Beckmann rearrangement. We confirmed that the acetylated ketoxime undergoes the Beckmann rearrangement with BF₃·Et₂O. The reaction of ketoximes with Koser’s reagent [PhI(OH)OTs] in the presence of tetrahydrofuran results in hydrolysis, affording the corresponding ketones in high yields at room temperature.

Key words

ketoximes - hypervalent iodine reagents - Beckmann rearrangement - hydrolysis - amides - ketones

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Supplementary Material

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