Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions
Kengo Hyodo*, Genna Hasegawa, Naoki Oishi, Kazuma Kuroda, Kingo Uchida
*Department of Material Chemistry, Faculty of Science and Technology, Ryukoku University, Seta, Otsu, Shiga 520-2194, Japan, Email: hyodorins.ryukoku.ac.jp
K. Hyodo, G. Hasegawa, N. Oishi, K. Kuroda, K. Uchida, J. Org. Chem., 2018, 83, 13080-13087.
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Brønsted acid catalysis enables a synthesis of secondary amides from ketones under mild conditions via transoximation and Beckmann rearrangement. In this reaction, O-protected oximes serve as more stable equivalents of explosive O-protected hydroxylamines. This method can be used for amide synthesis from α-branched alkyl aryl ketones. The presence of water is essential.
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proposed reaction pathway
Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
K. Hyodo, G. Hasegawa, H. Maki, K. Uchida, Org. Lett., 2019, 21, 2818-2822.
Beckmann Rearrangement, Amides