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）资助的。本项目将继续研究开发通过活化碳氢键和碳碳键直接形成碳氮键的新方法。在接下来的资助期内，催化氮化反应将有四个新的研究方向：1)硝基和亚硝基芳烃与亲亚硝基烯烃的环缩合反应，以及亚硝基芳烃/乙基-二羰基反应在构建吲哚咔唑骨架中的应用，这些反应是几类生物活性天然产物中常见的；2)确定配体辅助、铜催化的苯基胺化反应中间体和机制，扩大反应范围和用途，包括开发对映选择性变体；3)建立典型不反应饱和烃和芳烃的金属、Lewis酸和质子催化的氮化反应；4)发现能还原裂解偶氮化合物的金属配合物，从而确立偶氮化合物作为方便有效的氮化试剂的地位。一个协调的实验和计算程序将进行，以实现这些目标。有机和大分子化学项目用这个奖项来支持俄克拉何马大学化学和生物化学系的Kenneth M. Nicholas教授和他的同事们的研究。他的研究方向是发展新的催化反应和阐明其反应机理。这些新的催化反应将为几种有价值的有机氮产品提供新颖、直接和选择性的途径。导致这些化合物的金属介导过程从现成的起始材料开始，并且有望具有高度的区域和化学选择性，官能团耐受性，经济性，环保性，并且与现有方法互补或优于现有方法。此外，从这些研究中获得的产品在化学、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.