While aromatic diazonium salts are important reagents in organic synthesis, ‘Diazonium ions generated from ordinary aliphatic primary amines are usually useless for preparative purposes, since they lead to a mixture of products giving not only substitution by any nucleophile present, but also elimination and rearrangements if the substrate permits.’[1] In this work, we report that the statement is no longer valid, and it is now possible to control diazotization of aliphatic amines by utilizing isopentyl nitrite in HFIP. This transformation enabled electrophilic aromatic substitution with these highly abundant and commercially available alkyl reagents, as well as transforming them into building blocks typically employed in organic synthesis. The methodology opens an avenue for reactions involving aliphatic amines, even such demanding substrates as amino acids, as a source of carbocations thus expanding the degree of chemical space.

中文翻译：

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脂肪胺通过重氮化解锁用于选择性转化


虽然芳香族重氮盐是有机合成中的重要试剂，但“由普通脂肪族伯胺产生的重氮离子通常不可用于制备目的，因为它们会导致产物混合物不仅能被存在的任何亲核试剂取代，而且在底物允许的情况下还会消除和重排。[1] 在这项工作中，我们报告该声明不再有效，现在可以通过在 HFIP 中使用亚硝酸异戊酯来控制脂肪胺的重氮化。这种转化使这些高丰度和市售烷基试剂能够取代亲电芳烃，并将它们转化为有机合成中常用的结构单元。该方法为涉及脂肪胺的反应开辟了一条途径，甚至是氨基酸等要求苛刻的底物，作为碳阳离子的来源，从而扩大了化学空间的程度。