Synthesis of Dissymmetric Malonic Acid Monoamides from Symmetric Dithiomalonates
Synthesis of Dissymmetric Malonic Acid Monoamides from Symmetric Dithiomalonates
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DOI：
10.1002/slct.201601694
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发表时间：
2016-12
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影响因子：
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通讯作者：
H. Wauke;Kazumasa Matsuo;Kenji Matsumoto;M. Shindo
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文献类型：
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作者：
H. Wauke;Kazumasa Matsuo;Kenji Matsumoto;M. Shindo
报道了在温和条件下由对称的二硫代丙二酸酯高选择性合成不对称的S，N-丙二酸酯。使用我们开发的Cu（II）催化剂加速该反应。当使用脂肪胺作为亲核试剂时，胺也作为碱并且加速胺化反应。动力学研究表明，该反应的关键步骤是热生成酰基乙烯酮，其稳定性主要影响反应的选择性。不对称S，N-丙二酸酯的合成效用也通过合成linomide显示。
We report a highly selective synthesis of dissymmetric S,N-malonates from symmetric dithiomalonates under mild conditions. This reaction was accelerated using a Cu(II) catalyst developed by us. When an aliphatic amine was used as the nucleophile, the amine also worked as a base and accelerated the amination reaction. Kinetic studies indicated that the key step of this reaction is the thermal formation of an acylketene; its stability mainly contributes to the selectivity of the reaction. The synthetic utility of dissymmetric S,N-malonates is also shown by the synthesis of linomide.