Wu Kun, Huang Zhiliang, Qi Xiaotian, Li Yingzi, Zhang Guanghui, Liu Chao, Yi Hong, Meng Lingkui, Bunel Emilio E, Miller Jeffrey T, Pao Chih-Wen, Lee Jyh-Fu, Lan Yu, Lei Aiwen
College of Chemistry and Molecular Sciences, Institute for Advanced Studies, Wuhan University, Wuhan 430072, China.
College of Chemistry and Molecular Sciences, Institute for Advanced Studies, Wuhan University, Wuhan 430072, China. ; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA.
Sci Adv. 2015 Oct 9;1(9):e1500656. doi: 10.1126/sciadv.1500656. eCollection 2015 Oct.
Copper-catalyzed aerobic oxidative C-H/N-H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation.
为了合成多种吡嗪，开发了铜催化的简单酮与二胺之间的需氧氧化C-H/N-H偶联反应。各种取代酮都适用于这种转化。初步机理研究表明，该反应涉及自由基物种。X射线吸收精细结构实验表明，由两个距离为2.04 Å的N原子和两个距离较短为1.98 Å的O原子配位的Cu(II)物种5是这种需氧氧化偶联反应的活性物种。密度泛函理论计算表明，阳离子自由基的分子内偶联在这种转化中是有利的。
