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首页> 外文期刊>Chemistry: A European journal >QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design
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QM/MM modeling of enantioselective pybox-ruthenium- and box-copper-catalyzed cyclopropanation reactions: Scope, performance, and applications to ligand design

机译：对映选择性pybox-钌和box-copper催化的环丙烷化反应的QM / MM建模：范围，性能及其在配体设计中的应用

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摘要

An extensive comparison of full-QM (B3LYP) and QM/MM (B3LYP:UFF) levels of theory has been made for two enantioselective catalytic systems, namely, Pybox-Ru and Box-Cu complexes, in the cyclopropanation of alkenes (ethylene and styrene) with methyl diazoacetate. The geometries of the key reaction intermediates and transition structures calculated at the QM/MM level are generally in satisfactory agreement with full-QM calculated geometries. More importantly, the relative energies calculated at the QM/MM level are in good agreement with those calculated at the full-QM level in all cases. Furthermore, the QM/MM energies are often in better agreement with the stereoselectivity experimentally observed, and this suggests that QM/MM calculations can be superior to full-QM calculations when subtle differences in inter- and intramolecular interactions are important in determining the selectivity, as is the case in enantioselective catalysis. The predictive value of the model presented is validated by the explanation of the unusual enantioselectivity behavior exhibited by a new bis-oxazoline ligand, the stereogenic centers of which are quaternary carbon atoms.
机译：在烯烃（乙烯和乙烯苯乙烯）与重氮乙酸甲酯在QM / MM级别计算的关键反应中间体和过渡结构的几何形状通常与完全QM计算的几何形状令人满意。更重要的是，在所有情况下，以QM / MM级计算的相对能量与以全QM级计算的相对能量非常吻合。此外，QM / MM能量通常与实验观察到的立体选择性更好地吻合，这表明当分子间和分子间相互作用的细微差异对于确定选择性很重要时，QM / MM计算可能优于全QM计算，如对映选择性催化的情况。通过解释新的双恶唑啉配体所表现出的异常对映行为，证实了该模型的预测价值，所述双恶唑啉配体的立体发生中心为季碳原子。

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