King Amanda E, Brunold Thomas C, Stahl Shannon S
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2009 Apr 15;131(14):5044-5. doi: 10.1021/ja9006657.
Copper-catalyzed aerobic oxidative coupling of arylboronic acid derivatives and heteroatom nucleophiles is a highly useful method for the formation of aryl-heteroatom bonds. Mechanistic studies reveal that this reaction proceeds via an "oxidase"-style mechanism. Kinetic and spectroscopic studies establish that transmetalation of the aryl group from boron to Cu(II) is the turnover-limiting step and reoxidation of the reduced catalyst by O(2) is rapid. Further mechanistic analysis implicates the involvement of an aryl-copper(III) intermediate that undergoes facile C-O bond formation.
铜催化的芳基硼酸衍生物与杂原子亲核试剂的有氧氧化偶联反应是形成芳基-杂原子键的一种非常有用的方法。机理研究表明，该反应通过“氧化酶”式机理进行。动力学和光谱研究表明，芳基从硼到铜（II）的转金属化是限速步骤，而被还原的催化剂被氧气快速再氧化。进一步的机理分析表明，涉及一个易于形成碳-氧键的芳基-铜（III）中间体。
