Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel.
Chemistry. 2011 Jun 27;17(27):7623-31. doi: 10.1002/chem.201002724. Epub 2011 May 18.
The new approach for palladium-catalyzed cross-coupling of two non-activated aromatic compounds (D. R. Stuart, K. Fagnou, Science 2007, 316, 1172) was studied theoretically. The energetic span model (S. Kozuch, S. Shaik, Acc. Chem. Res. 2011, 44, 101, and references therein) was employed to analyze the kinetic behavior of the catalytic cycle. The computed energy profile, combined with the energetic span model, accounts for the experimental selectivity, which favors the hetero-coupling of benzene with indole. This selectivity is driven by a fine balance of the entropic contributions and the high ratio of concentrations used for benzene over indole. This analysis may allow future theoretical predictions of how different aromatic compounds can be effectively coupled.
新型钯催化的两种非活化芳香族化合物交叉偶联方法（D. R. Stuart, K. Fagnou, Science 2007, 316, 1172）已被理论研究。能隙跨度模型（S. Kozuch, S. Shaik, Acc. Chem. Res. 2011, 44, 101, 及其中参考文献）被用来分析催化循环的动力学行为。计算出的能量曲线，与能隙跨度模型相结合，解释了实验的选择性，这有利于苯与吲哚的杂偶联。这种选择性是由熵贡献的精细平衡和苯与吲哚的高浓度比驱动的。这种分析可能允许未来对不同芳香族化合物如何有效偶联的理论预测。
