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使用水作为氧原子源,实现环状胺到内酰胺和 H2 的无氧化剂转化。

Oxidant-free conversion of cyclic amines to lactams and H2 using water as the oxygen atom source.

机构信息

Department of Organic Chemistry, Weizmann Institute of Science , Rehovot, 76100, Israel.

出版信息

J Am Chem Soc. 2014 Feb 26;136(8):2998-3001. doi: 10.1021/ja500026m. Epub 2014 Feb 18.

Abstract

Direct conversion of cyclic amines to lactams utilizing water as the only reagent is catalyzed by pincer complex 2. In contrast to previously known methods of amine-to-amide conversion, this reaction occurs in the absence of oxidants and is accompanied by liberation of H2, with water serving as a source of oxygen atom. Formation of a cyclic hemiaminal intermediate plays a key role in enabling such reactivity. This represents an unprecedented, conceptually new type of amide formation reaction directly from amines and water under oxidant-free conditions.

摘要

手性双氮钳配合物 2 可催化仅用水作为唯一试剂将环胺直接转化为内酰胺。与先前已知的胺到酰胺的转化方法不同,该反应在没有氧化剂的情况下发生,并伴随着 H2 的释放,水作为氧原子的来源。形成环状半亚胺中间体在实现这种反应性方面起着关键作用。这代表了在无氧化剂条件下,胺和水直接形成酰胺的一种前所未有的新概念的反应。

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