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Synthesis 2022; 54(18): 4095-4103
DOI: 10.1055/a-1835-2188
DOI: 10.1055/a-1835-2188
paper
The Reaction of Ketoximes with Hypervalent Iodine Reagents: Beckmann Rearrangement and Hydrolysis to Ketones
This work was financially supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant Numbers 19K16329 and 18K05132, and also supported by a 2021 Kindai University Research Enhancement Grant (KD2106).
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 - ketonesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1835-2188
- Supporting Information
Publication History
Received: 12 March 2022
Accepted after revision: 26 April 2022
Accepted Manuscript online:
26 April 2022
Article published online:
08 June 2022
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