Catalytic Nitrogenation of Hydrocarbons

该奖项是根据2009年《美国复苏和再投资法案》(公法111-5)提供资金的。该项目将继续研究开发通过活化C-H键和C-C键直接形成C-N键的新方法。催化氮化反应的四个新方面将在下一个资助期间进行研究：1)硝基和亚硝基芳烃与烯类亚硝酸酯的环缩合反应，以及亚硝基/乙酰基-α-二羰基反应在构建几类生物有效天然产物共同的吲哚咔唑骨架中的应用；2)确定配体辅助的铜催化的苯胺化反应的反应中间体和机理，并扩大反应范围和用途，包括开发对映异构体；3)建立金属、路易斯酸和质子催化的典型的非活性和碳氢化合物的氮化反应；4)发现了能够还原裂解偶氮化合物的金属络合物，为偶氮化合物成为方便有效的氮化试剂奠定了基础。为了实现这些目标，将进行一项协调的实验和计算计划。通过这一奖项，有机化学和高分子化学项目正在支持俄克拉荷马大学化学和生物化学系的Kenneth M.Nicholas教授和他的同事的研究。尼古拉斯教授的研究项目侧重于开发新的催化反应并阐明其反应机理。这些新的催化反应将为几类有价值的有机氮产品提供新的、直接的和选择性的路线。金属介导法合成这些化合物的原料很容易获得，并且有望具有高度的区域和化学选择性、耐受官能团、经济、环境友好以及与现有方法互补或优于现有方法。此外，这些研究得出的产品在化学、技术和社会方面都具有巨大的价值。

This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5). This project will continue studies on the development of new methods for the direct formation of C-N bonds via activation of C-H and C-C bonds. Four new aspects of catalytic nitrogenation reactions are targeted for study during the next funding period: 1) cyclocondensations of nitro- and nitrosoarenes with olefinic nitrosophiles and application of nitrosoarene/acetylenic alpha-dicarbonyl reactions in the construction of the indolocarbazole skeleton common to several classes of biologically-potent natural products; 2) identifying the reactive intermediates and mechanism of ligand-assisted, copper-catalyzed benzylic aminations, and expanding the reaction scope and utility, including the development of enantioselective variants; 3) establishing metal-, Lewis acid- and proton-catalyzed nitrogenation reactions of typically unreactive saturated and aromatic hydrocarbons; and 4) finding metal complexes capable of reductive cleavage of azo compounds leading the way to establish azo compounds as convenient and effective nitrogenation reagents. A coordinated experimental and computational program will be conducted to accomplish these objectives. With this award the Organic and Macromolecular Chemistry Program is supporting the research of Professor Kenneth M. Nicholas and his co-workers of the Department of Chemistry and Biochemistry at the University of Oklahoma. Prof. Nicholas' research programs focus on the development of new catalytic reactions and elucidation of their reaction mechanisms. These new catalytic reactions will provide novel, direct, and selective routes to several classes of valuable organonitrogen products. The metal-mediated processes leading to these compounds proceed from readily available starting materials and are expected to be highly regio- and chemoselective, functional group tolerant, economical, environmentally benign, and complementary or superior to existing methods. Moreover, the products derived from these studies are of immense value chemically, technologically, and societally.