Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions
Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions
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DOI：
10.1021/acs.joc.8b01810
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发表时间：
2018-11-02
影响因子：
3.6
通讯作者：
Uchida, Kingo
中科院分区：
文献类型：
--
作者：
Hyodo, Kengo;Hasegawa, Genna;Uchida, Kingo
在温和条件下，以酮为原料，经溴代酸催化的氧保护肟为爆炸性氧保护羟胺的稳定替代物，通过肟基转移反应和贝克曼重排反应合成了仲酰胺。该方法可应用于从α-支化烷基芳基酮的高重复选择性酰胺合成，并在1-g规模上进行。水的存在是这个反应必不可少的，它的作用是由同位素标记实验澄清。
The Bronsted acid-catalyzed synthesis of secondary amides from ketones under mild conditions is described via transoximation and Beckmann rearrangement using O-protected oximes as more stable equivalents of explosive O-protected hydroxylamines. This methodology could be applied to highly rearrangement-selective amide synthesis from alpha-branched alkyl aryl ketones and performed on a 1-g scale. The presence of water is essential for this reaction, and its role was clarified by isotope-labeling experiments.