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

项目摘要/摘要 由于广泛的含氮化合物具有生物活性，新的开发 C-N键的形成方法是合成有机化学的核心挑战。这一发现 用于有机反应的催化剂通常是可取的，因为从以下观点来看，它们可以提供优势 效率/经济性。 这项建议旨在发现金属催化的C-N键形成的新方法。 通过使用自由基途径的光诱导铜催化，我们计划扩大N- 烷基化反应远远超过SN2反应所提供的反应。这些偶联反应预计将继续进行 在异常温和的条件下，要有广泛的适用性来产生不同的氮家族- 含有化合物，并具有良好的立体选择性(如果适用)。研究计划还包括 描述机理研究(例如，同位素标记、立体化学、质谱学和电子 顺磁共振波谱)，这将提供对这些新的反应途径的洞察 光诱导，铜催化的C-N键形成反应。这些机械性的调查将起到 在促进我们的反应发展计划以及拓宽我们对 基本的化学反应。

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.