绿色催化羟基化和环加成反应机理的计算研究

绿色催化反应是一类符合绿色化学原则的环保和高效的反应，反应物和生成物均为对环境毒性较低或者无环境毒性的化学品，具有反应条件温和、原子经济性高和环境友好的特点。发展绿色催化反应对人类的健康和环境保护具有重要意义。羟基化反应和环加成反应作为常用的有机合成方法，发展其绿色合成也是至关重要。目前，第一周期过渡金属催化和光酶催化的绿色羟基化反应和环加成反应已经有不少报道，但是相关的反应机理研究并不充分。因此，本文选取了四个绿色催化的羟基化反应和环加成反应，采用了计算化学的研究方法，对反应的机理进行了系统的研究。

本文通过多尺度模拟的方法（密度泛函理论（DFT）与量子力学/分子力学（QM/MM）方法），采用小分子模型、簇模型和全蛋白体系，对XOM光酶催化羟基化反应进行了深入的研究。计算结果揭示了反应通过两步基元反应完成，氢原子转移步骤为反应速率决定步，提出了在原光敏剂的羰基g位用N原子取代C原子会使得反应中间体和产物形成分子内氢键而更加稳定，可以使得反应在热力学上更加有利。光催化与酶催化结合的方法提高了酶催化的效率，并且对环境友好，符合绿色化学理念。然而，目前酶催化剂种类较少，并且酶催化剂对于温度和pH等条件较为敏感，在工业应用上仍有所局限。相比之下，过渡金属催化剂通常具有更好的化学稳定性和热稳定性。

因此，为了更深入地探究绿色催化羟基化反应机理，本文使用DFT方法对钛/钴双金属催化环氧化合物异构化为烯丙基醇的羟基化反应进行了详细的计算研究，阐明了反应机理，揭示了钛和钴双金属共同作用催化了关键的氢原子转移决速步，该步骤涉及三重态到单重态的双态反应性，在降低反应能垒和稳定产物方面起到了重要的作用。反应过程中的其他步骤通过单金属催化的形式进行，虽然双金属催化过程中存在有利的色散相互作用，但是却存在较高的熵损失，不利于双金属催化过程的发生。此外，本文选取了双锌催化的丙二酸酯的选择性羟基化反应进行了深入的DFT计算研究，揭示了该反应中关键的负氢转移步骤是通过直接的氢负离子转移机理，即Zn-H键上的氢负离子直接作为亲核试剂进攻丙二酸酯的一个羰基碳原子，完成丙二酸酯的羟基化。通过对映选择性分析，阐明了影响该反应立体选择性的因素包括底物与配体之间的位阻效应、底物与配体的p-p堆积等。

绿色催化环加成反应也是一类重要的合成反应，为了探究绿色催化环加成反应机理，本文对铜催化的非活化烯烃的1,3-偶极环加成反应进行了DFT计算研究，阐明了环加成通过两步基元反应完成，并且第二步环化过程为决速步。另外，揭示了影响反应区域选择性的主要因素是产物的稳定性，预测了8,8-二甲基异苯并富烯发生[3+6]环加成反应，说明了过渡态结构中的位阻效应和不同过渡态的扭曲能的差异是影响反应区域选择性、立体选择性和化学选择性的原因。

综上所述，本文利用计算化学方法深入研究了绿色羟基化和环加成反应的机理，为理解光酶催化以及过渡金属催化的反应机理，尤其是双金属催化的反应机理提供了重要的理论见解，这些计算研究的成果不仅有助于优化反应条件，提高反应效率，同时也为指导设计新型绿色可持续发展的催化体系提供了理论依据。

Hydroxylation and cycloaddition reactions are important organic synthesis reactions. Meanwhile, development of environmentally-friendly catalysis is essential for the sustainable manufactory. In this dissertation, computational chemistry has been used to examine the reaction mechanisms of transition metal-catalyzed hydroxylation, photoenzyme-catalyzed hydroxylation, as well as transition metal-catalyzed 1,3-dipole cycloaddition.

Hydroxylation reaction catalyzed by XOM photoenzyme was studied in-depth by multi-scale simulations. The computational results reveal that the reaction is completed by a two-step process, in which the hydrogen atom transfer step is the rate-determining step. The substitution of C_g atom of the carbonyl group by N atom in the XOM photosensitizer is proposed to form an intramolecular H-bond in the product, which can make the reaction more thermodynamically favorable.

In order to further explore the mechanism of green catalytic hydroxylation reaction, a DFT study of a synergistic bimetallic Ti/Co-catalyzed epoxide isomerization reaction to form a hydroxyl group is investigated in detail. The DFT results clarify reaction mechanism, and reveal that the bimetallic-catalyzed hydrogen atom transfer (HAT) step is the rate-determining step in the reaction. This HAT step also involves the two-state reactivity switching from triplet state to singlet state. Moreover, such two-state reactivity plays an important role in reducing the energy barrier and enhancing the stability of the product. Moreover, the other steps were found to be carried out in the form of monometallic catalysis instead of bimetallic process. Although there are favorable dispersion interactions in the bimetallic catalytic process, it experiences a higher entropy loss, which is the key to disfavor the bimetallic catalytic process.

In addition, a DFT study on di-Zn metal-catalyzed desymmetrization of malonate esters to form a hydroxyl group is presented. The key hydride transfer step in the reaction is revealed to occur through the direct hydride transfer mechanism, in which the hydride on the Zn-H bond directly attacks a carbonyl carbon atom of the malonate as a nucleophile to complete the desymmetrization of the malonate. Through enantio-selectivity analysis, the factors affecting the stereo-selectivity of the reaction were explored.

To reveal the mechanism of green catalytic cycloaddition reaction, a reaction mechanism for a Cu-catalyzed 1,3-dipolar cycloaddition of unactivated alkenes was studied. It was clarified that the cycloaddition was completed by a two-step mechanism, and the second step of cyclization was the rate-determining step. Then, the reasons affecting the regio-, stereo- and chemo-selectivity of the reaction were revealed, in which the stability of the products play the key factor. Futhermore, 8,8-dimethylisobenzofulvene is predicted to undergo [3+6] cycloaddition reaction in the same catalytic system.

In summary, computational chemistry methods were applied to investigate the reaction mechanisms of green hydroxylation and cycloaddition, which provides important theoretical insights for understanding the reaction mechanism catalyzed by photoenzyme and transition metals (especially the reaction mechanisms catalyzed by bimetallic systems) as well as hopefully guide the design of new green and sustainable catalytic systems.

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