Uranium metallacycle [cyclic] [(Me3Si)2N]2UCH2SiMe2NSiMe3: a mild reagent for the synthesis of methyl ketones from nitriles
Uranium metallacycle [cyclic] [(Me3Si)2N]2UCH2SiMe2NSiMe3: a mild reagent for the synthesis of methyl ketones from nitriles
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DOI：
10.1021/jo00276a046
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发表时间：
1989-07
影响因子：
3.6
通讯作者：
A. Dormond;A. Elbouadili;C. Moïse
中科院分区：
文献类型：
--
作者：
A. Dormond;A. Elbouadili;C. Moïse
腈与格氏试剂反应是合成酮亚胺的一条广泛应用的路线，酮亚胺经水解可得到酮。然而，该反应受到一些限制。对于脂族腈，由于{α}-氢原子的酸性而产生严重的复杂性。如果使用强碱性溶剂，它们会与腈竞争形成有机镁复合物。如果使用有机锂试剂代替格利雅试剂，锂试剂和产物酮亚胺盐的碱性都更大，会导致更大的困难。本文报道了在非碱性溶剂中用铀金属配合物1使腈类化合物发生特异、快速、清洁和高产率的反应生成相应的甲基酮。
The reaction of nitriles with Grignard reagents is a widely applicable synthetic route to ketimines, which by facile hydrolysis give ketones. However, this reaction suffers some limitations. With aliphatic nitriles, a serious complication arises due to the acidity of the {alpha}-hydrogen atom. If strongly basic solvents are used, they compete with the nitrile in formation of an organomagnesium complex. If organolithium reagents are used instead of Grignard reagents, the greater basicity of both lithium reagent and the product ketimine salt causes even more difficulty. We report here a specific, rapid, clean, and high-yield reaction of nitriles to give the corresponding methyl ketones by using the uranium metallacycle 1 in nonbasic solvents.