Transition Metal-Catalyzed Nitrogenation of Hydrocarbons

胺和n -杂环的重要性，无论是作为合成中间体还是作为最终产物，使得新的，高效和选择性的C-N键形成反应的发生成为一个重要的目标。过渡金属介导的反应选择性地从C-C不饱和产生新的C-C、C-O和C-H键，极大地提高了有机合成的能力，但过渡金属促进相应的C-N键形成（氮化）的潜力才刚刚开始实现。该项目响应了双重需求：1)合成有机氮化合物的新选择方法，2)对有机氮碎片与金属中心配合的反应性的新认识。最近发现的两个反应将在项目期间进行详细的研究：1)有机金属催化的氮有机物的烯丙基胺化；2)硝基和亚硝基芳烃与炔烃还原环化，生成吲哚和其他杂环。机制分析将阐明所涉及的活性胺化物种的性质，而合成研究将提供一些重要的含氮产品，包括吲哚生物碱的潜在前体。许多具有生物或医学意义的有机化合物都含有氮原子。开发高效、选择性和催化的方法将氮引入有机分子仍然是一个重要的研究目标。奥克拉荷马大学（诺曼校区）化学与生物化学系的Kenneth M. Nicholas教授，因其对碳氢化合物氮化的研究而获得有机与大分子化学项目的资助。尼古拉斯教授发现了一系列不寻常的金属催化反应，每一个都为有价值的含氮有机产品提供了一条新颖而直接的途径。导致这些化合物的金属介导的工艺从易于获得的起始材料开始，并且有望具有高度选择性、通用性和互补或优于现有方法。新的高效、经济、环保的氮化工艺也可能用于化学和制药工业。该项目还将成为在化学合成和催化的基础和技术关键领域对本科生、研究生和博士后进行教育和技术培训的有效工具。

The importance of amines and N-heterocycles, both as synthetic intermediates and as end-products, makes the genesis of new, efficient and selective C-N bond-forming reactions an important objective. Transition metal-mediated reactions which selectively produce new C-C, C-O and C-H bonds from C-C unsaturation have dramatically increased the power of organic synthesis, but the potential of transition metals to facilitate corresponding C-N bond formation (nitrogenation) is just beginning to be realized. This project responds to a dual need: 1) for new selective methods for the synthesis of organonitrogen compounds and 2) for new understanding of the reactivity of organonitrogen fragments coordinated to metal centers. Two recently discovered reactions are targeted for detailed study during the project period: 1) organometal-catalyzed allylic aminations by nitroorganics; and 2) reductive annulation of nitro- and nitrosoarenes with alkynes to produce indoles and other heterocycles. Mechanistic analysis will elucidate the nature of the active aminating species involved, while synthetic studies will provide access to a number of important nitrogen-containing products, including potential precursors for the indole alkaloids.Numerous organic compounds of biological or medicinal importance contain nitrogen atoms. The development of efficient, selective, and catalytic methods for the introduction of nitrogen into organic molecules remains a significant research objective. Professor Kenneth M. Nicholas, of the Department of Chemistry and Biochemistry at the University of Oklahoma (Norman Campus), is supported by the Organic and Macromolecular Chemistry Program for his studies of the nitrogenation of hydrocarbons. Professor Nicholas has discovered a series of unusual metal-catalyzed reactions, each of which provides a novel and direct route to valuable nitrogen-containing organic products. The metal-mediated processes leading to these compounds proceed from readily available starting materials and are expected to be highly selective, versatile, and complementary or superior to existing methods. New efficient, economical, and environmentally-friendly nitrogenation processes for the chemical and pharmaceutical industries also could result. This project also will serve as an effective vehicle for the education and technical training of undergraduate, graduate and postdoctoral students in the fundamentally and technologically critical areas of chemical synthesis and catalysis.