PHOTOINDUCED, COPPER-CATALYZED SUBSTITUTION REACTIONS OF ALKYL ELECTROPHILES BY NITROGEN NUCLEOPHILES

项目总结/摘要 由于广泛的含氮化合物表现出生物活性，因此新的含氮化合物的开发是必要的。 形成C-N键的方法是合成有机化学中的主要挑战。发现 有机反应的催化剂通常是理想的，因为它们可以从以下角度提供优点： 效率/经济。 该提议旨在发现金属催化C-N键形成的新方法。 通过使用光诱导铜催化通过自由基途径，我们计划扩大范围的N- 烷基化反应远远超过了SN 2反应所提供的。预计这些偶联反应将继续进行 在异常温和的条件下，具有广泛的适用性，用于产生不同的氮族- 含有化合物，并以良好的立体选择性进行（当适用时）。研究计划还 描述了机理研究（例如，同位素标记、立体化学、质谱和电子 顺磁共振光谱），这将提供深入了解这些新的反应途径 光诱导的铜催化的C-N键形成反应。这些机械研究将发挥 在促进我们的反应发展计划，以及扩大我们的理解， 基本化学反应性。

PROJECT SUMMARY/ABSTRACT Because a wide array of nitrogen-containing compounds exhibit bioactivity, the development of new methods for the formation of C–N bonds is a central challenge in synthetic organic chemistry. The discovery of catalysts for organic reactions is often desirable, since they can offer advantages from the standpoints of efficiency/economy. This proposal is directed at the discovery of new methods for metal-catalyzed C–N bond formation. Through the use of photoinduced copper catalysis via a radical pathway, we plan to expand the scope of N- alkylations well beyond that provided by SN2 reactions. These coupling reactions are anticipated to proceed under unusually mild conditions, to have broad applicability for the generation of diverse families of nitrogen- containing compounds, and to proceed with good stereoselectivity (when applicable). The research plan also describes mechanistic studies (e.g., isotopic labeling, stereochemical, mass spectrometry, and electron paramagnetic resonance spectroscopy) that will provide insight into the novel reaction pathways of these photoinduced, copper-catalyzed C–N bond-forming reactions. These mechanistic investigations will play an important role in facilitating our reaction-development program, as well as broadening our understanding of fundamental chemical reactivity.