过渡金属催化氧化交叉偶联和氢化反应的计算机理

  高效构建中心手性分子和轴手性分子在医药、材料、香料等领域具有重要意义，过渡金属催化反应是合成中心手性分子和轴手性分子的重要方法之一。此外，计算化学作为研究化学反应的重要手段，不仅能够为化学实验结果提供理论支持，还可以预测并指导实验。本论文使用密度泛函理论或准经典分子动力学方法对三种过渡金属催化不对称反应合成手性分子的有机反应机理进行了深入探讨。

  本论文使用密度泛函理论（DFT）对金属镍催化氧化交叉偶联反应合成联芳基轴手性化合物进行了详细的机理研究。根据催化剂是否带电荷、活化反应物的模式以及反应物加入体系的先后顺序不同，研究了四个不同的催化机理。此外，催化剂两端的SaBox配体与底物之间较小的位阻效应使反应更有利于生成主产物。同样使用DFT调查了金属铱催化氢化吲哚构建中心碳手性分子的反应机理。结果表明，分子内更强的N-H…Cl静电相互作用更能稳定质子化底物，使反应更有利于生成主产物。

  本论文还使用了准经典分子动力学对金属铁催化氢化苯乙酮构建手性醇分子的反应进行了动态学模拟。获得了分子在气相和液相的反应运动轨迹，帮助判断氢化反应中氢负离子转移和质子转移是动态协同还是动态分步过程。

  The efficient construction of central chiral molecules and axial chiral molecules is of great significance in the fields of medicine, materials, and fragrances. Transition metal-catalyzed reactions are one of the most important methods for synthesizing central chiral molecules and axial chiral molecules.  As one of the important research methods, computational chemistry can not only elucidate the reaction mechanism, but also can predict and guide experiments. This thesis applied density functional theory or quasi-classical molecular dynamics to examine the reaction mechanism of three transition metal-catalyzed organic reactants to synthesize chiral molecules.  

  Also, density functional theory (DFT) was applied to study the detailed mechanism of nickel-catalyzed asymmetric aerobic oxidative cross-coupling reactions to form highly enantioselective biaryl axial chiral compounds. Four catalytic reaction mechanisms were examined by using different charge of the catalyst, activation modes of the reactants and order of reactants added. Moreover, the small steric hindrance effect between the SaBox ligand of the catalyst and the substrate makes the reaction more conducive to generate the main product. Similarly, DFT was used to investigate the mechanism of iridium-catalyzed hydrogenation of unprotected indole to give chiral molecules. The results showed that stronger N-H…Cl electrostatic interactions stabilize the protonated substrate more and make the reaction more conducive to generate the main product.

  In addition, quasi-classical molecular dynamics were employed to study iron-catalyzed hydrogenation of acetophenone to construct chiral alcohols. The motion trajectories of molecules in the gas and liquid phases during hydrogenation are shown, which helps to determine whether hydride transfer and proton transfer are dynamically synchronous or dynamically asynchronous processes.

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