Practical Singly and Doubly Electrophilic Aminating Agents: A New, More Sustainable Platform for Carbon-Nitrogen Bond Formation
Practical Singly and Doubly Electrophilic Aminating Agents: A New, More Sustainable Platform for Carbon-Nitrogen Bond Formation
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实用的单亲电胺化剂和双亲电胺化剂：一种新的、更可持续的碳氮键形成平台
DOI：
10.1021/jacs.7b05279
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发表时间：
2017-08-16
影响因子：
15
通讯作者：
Kurti, Laszlo
中科院分区：
文献类型：
--
作者：
Kattamuri, Padmanabha V.;Yin, Jun;Kurti, Laszlo
鉴于胺在大量具有生物活性的天然产物、活性药物成分、农用化学品和功能材料中的重要性，开发具有广泛底物范围的有效C-N键形成方法仍然是合成有机化学研究的前沿。在这里，我们提出了一个一般的和根本上新的合成方法，直接，过渡金属的制备对称和不对称的二芳基，芳烷基，和二烷基胺，依赖于容易的单或双加成容易获得的C-亲核试剂的氮原子的工作台稳定的亲电胺化剂。实际的单极性和双极性反转（即，使用空间和电子可调的酮丙二酸酯衍生的亚胺和肟实现氮原子的取代。总的来说，这种新的方法代表了一种操作简单，可扩展和环境友好的替代过渡金属催化的C-N交叉偶联方法，目前用于获得结构多样的仲胺。
Given the importance of amines in a large number of biologically active natural products, active pharmaceutical ingredients, agrochemicals, and functional materials, the development of efficient C-N bond-forming methods with wide substrate scope continues to be at the frontier of research in synthetic organic chemistry. Here, we present a general and fundamentally new synthetic approach for the direct, transition-metal-free preparation of symmetrical and unsymmetrical diaryl-, arylalkyl-, and dialkylamines that relies on the facile single or double addition of readily available C-nucleophiles to the nitrogen atom of bench-stable electrophilic aminating agents. Practical single and double polarity reversal (i.e., umpolung) Of the nitrogen atom is achieved using sterically and electronically tunable ketomalonate-derived imines and oximes. Overall, this novel approach represents an operationally simple, scalable, and environmentally friendly alternative to transition-metal-catalyzed C-N cross-coupling methods that are currently used to access structurally diverse secondary amines.