Cross-Coupling of Secondary Amides with Tertiary Amides: The Use of Tertiary Amides as Surrogates of Alkyl Carbanions for Ketone Synthesis
Cross-Coupling of Secondary Amides with Tertiary Amides: The Use of Tertiary Amides as Surrogates of Alkyl Carbanions for Ketone Synthesis
复制标题
仲酰胺与叔酰胺的交叉偶联：使用叔酰胺作为烷基碳负离子的替代物用于酮合成
DOI：
10.1002/cjoc.201900215
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发表时间：
2019
影响因子：
5.4
通讯作者：
Huang Pei-Qiang
中科院分区：
文献类型：
--
作者：
Wang Shu-Ren;Huang Pei-Qiang
主要观察和结论近年来，在酰胺的直接转化领域取得了令人振奋的进展，但两个酰胺之间的缩合仍然很少见，仅限于同位偶联反应。在这里，我们报道了仲酰胺和叔胺的交叉偶联，这提供了在温和的条件下合成酮，并以叔胺作为烷基碳负离子的替代品的特点。该方法依赖于叔胺在Vaska催化剂上催化部分还原生成的烯胺与仲酰胺经三氟甲磺酸活化生成的氮离子的偶联，以及随后的脱甲酰化反应。
Summary of main observation and conclusionIn recent years, exciting progress has been made in the field of direct transformation of amides, nevertheless, the condensation between two amides remains rare and restricted to homo‐coupling reactions. Herein, we report the cross‐coupling of secondary amides with tertiary amides, which provides a synthesis of ketones under mild conditions, and features the use of tertiary amides as surrogates of alkyl carbanions. The method relies on the coupling of enamines, generated from tertiary amides by catalytic partial reduction of tertiary amides with Vaska's catalyst, with nitrilium ions, formedin situfrom secondary amides via activation with trifluoromethanesulfonic anhydride, and on the subsequent deformylation.