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首页> 外文期刊>Chemistry: A European journal >Insights into Sonogashira cross-coupling by high-throughput kinetics and descriptor modeling
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Insights into Sonogashira cross-coupling by high-throughput kinetics and descriptor modeling

机译：高通量动力学和描述符建模对Sonogashira交叉耦合的洞察

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摘要

A method is presented for the high-throughput monitoring of reaction kinetics in homogeneous catalysis, running up to 25 coupling reactions in a single reaction vessel. This method is demonstrated and validated on the Sonogashira reaction, analyzing the kinetics for almost 500 coupling reactions. First, one-pot reactions of phenylacetylene with a set of 20 different meta- and para-substituted aryl bromides were analyzed in the presence of 17 different Pd-phosphine complexes. In addition, the temperature-dependent Sonogashira reactions were examined for 21 different ArX (X=Cl, Br, I) substrates, and the corresponding activation enthalpies and entropies were determined by means of Eyring plots: ArI (Delta H-double dagger = 48-62 kJ mol(-1); Delta S* = -71--39 Jmol(-1) K; NO2 -> OMe), ArBr (Delta H-double dagger=54-82 kJmol(-1), Delta S-double dagger = -55-11 Jmol(-1) K), and ArCl (Delta H-double dagger = 95-144 kJ mol(-1), Delta S-double dagger = -6-100 J mol(-1) K). DFT calculations established a linear correlation of Delta H* and the Kohn-Sham HOMO energies of ArX (X = Cl, Br, I) and confirmed their involvement in the rate-limiting step. However, despite different C-X bond energies, aryl iodides and electron-deficient aryl bromides showed similar activation parameters.
机译：提出了一种用于高通量监测均相催化反应动力学的方法，在一个反应​​容器中最多可进行25个偶联反应。该方法已在Sonogashira反应中得到证实和验证，并分析了近500个偶联反应的动力学。首先，在存在17种不同的Pd-膦配合物的情况下，分析了苯乙炔与20种不同的间位和对位取代的芳基溴的一锅反应。此外，检查了21种不同ArX（X = Cl，Br，I）底物的温度依赖性Sonogashira反应，并通过Eyring曲线确定了相应的活化焓和熵：ArI（Delta H-double dagger = 48 -62 kJ mol（-1）; Delta S * = -71--39 Jmol（-1）K; NO2-> OMe），ArBr（Delta H-双匕首= 54-82 kJmol（-1），Delta S -双匕首= -55-11 Jmol（-1）K）和ArCl（Delta H-双匕首= 95-144 kJ mol（-1），Delta S-双匕首= -6-100 J mol（-1 ）K）。 DFT计算建立了Delta H *与ArX的Kohn-Sham HOMO能量（X = Cl，Br，I）的线性相关性，并证实了它们参与了限速步骤。但是，尽管C-X键能不同，但芳基碘化物和缺电子的芳基溴化物显示出相似的活化参数。

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