Strieter Eric R, Bhayana Brijesh, Buchwald Stephen L
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
J Am Chem Soc. 2009 Jan 14;131(1):78-88. doi: 10.1021/ja0781893.
The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggests that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation.
铜催化的酰胺N-芳基化反应，即戈德堡反应，是一种构建与工业和学术领域相关产物的有效方法。在此，我们展示了有关酰胺催化和化学计量N-芳基化反应的机理细节。在催化反应的背景下，我们的研究结果揭示了螯合二胺配体在控制活性催化物种浓度方面的重要性。催化和化学计量结果之间的一致性表明，芳基卤化物的活化是通过1,2-二胺配位的铜（I）酰胺配合物发生的。使用1,2-二胺配位的Cu（I）酰胺对芳基碘化物的化学计量N-芳基化反应的动力学研究也为芳基卤化物活化机理提供了见解。
