Department of Chemistry, Northeast Normal University, Changchun 130024, China.
Org Lett. 2011 Dec 16;13(24):6536-9. doi: 10.1021/ol2028288. Epub 2011 Nov 11.
A novel copper-mediated chelation-assisted ortho C-H nitration of (hetero)arenes has been developed for the first time, which used dioxygen as terminal oxidant and 1,2,3-TCP as solvent, leading to the synthesis of nitroaromatics with excellent regioselectivity and in good yields. Mechanistic investigations indicate a mechanism involving a four-centered transition state, with simultaneous cleavage of an ortho C-H bond and a N-O bond of the nitrate anion on the 2-arylpyridine-coordinated copper(II) complex.
首次开发了一种新型的铜介导螯合辅助的（杂）芳基邻位 C-H 硝化反应，该反应以氧气为末端氧化剂，1,2,3-TCP 为溶剂，以优异的区域选择性和良好的收率合成了硝基芳烃。机理研究表明，该反应涉及一个四中心过渡态，同时断裂 2-芳基吡啶配位的铜（II）配合物上的邻位 C-H 键和硝酸盐阴离子的 N-O 键。
