Transition Metal-Catalyzed Nitrogenation of Hydrocarbons

胺和N-杂环作为合成中间体和最终产物的重要性使得新的、有效的和选择性的C-N键形成反应的发生成为重要目标。过渡金属介导的从C-C不饱和键选择性地产生新的C-C、C-O和C-H键的反应显著地提高了有机合成的能力，但是过渡金属促进相应的C-N键形成（氮化）的潜力才刚刚开始被认识。该项目响应了双重需求：1）合成有机氮化合物的新选择性方法和2）对与金属中心配位的有机氮片段的反应性的新理解。在项目期间，针对两个最近发现的反应进行详细研究：1）硝基有机物催化的烯丙基胺化; 2）硝基和亚硝基芳烃与炔的还原成环反应，以产生吲哚和其他杂环。机理分析将阐明所涉及的活性胺化物种的性质，而合成研究将提供许多重要的含氮产物，包括吲哚生物碱的潜在前体。许多具有生物或医学重要性的有机化合物含有氮原子。开发高效、选择性和催化性的方法将氮引入有机分子中仍然是一个重要的研究目标。Kenneth M.尼古拉斯，化学和生物化学系在俄克拉荷马州（诺曼校区）的大学，是由有机和大分子化学计划的支持，他的研究碳氢化合物的氮化。尼古拉斯教授发现了一系列不寻常的金属催化反应，每一种反应都提供了一种新颖而直接的途径来获得有价值的含氮有机产品。产生这些化合物的金属介导的方法从容易获得的起始材料进行，并且预期是高度选择性的、通用的，并且是现有方法的补充或上级。新的高效，经济和环境友好的氮化工艺也可能导致化学和制药工业。该项目还将作为本科生，研究生和博士后学生在化学合成和催化的基本和技术关键领域的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.