碳-碳键构建反应机理的计算研究

碳-碳键的构建是有机合成化学的核心研究。本论文采用密度泛函理论 （DFT），对三种不同催化体系（过渡金属催化、有机催化和生物催化） 下构建碳-碳键的反应机理和选择性进行研究，旨在为开发新型的碳-碳键构 建策略提供理论指导。 在过渡金属 Rh(I)-卡宾催化不对称吲哚 C-H 键官能团化构建碳-碳键的 反应体系中，揭示了反应的热力学与动力学特征，确定还原消除步骤为反 应决速步。通过对卡宾与二烯配体之间配位模式的分析，阐述了手性二烯 配体与卡宾配体之间的空间位阻以及电子效应在对映选择性上的决定性作 用。在有机手性双硼试剂介导的酮亚胺不对称还原自身偶联构建碳-碳键的 体系中，对关键的协同[3,3]-σ 重排反应机理过渡态进行分析，揭示了双硼 与底物的配位模式、空间位阻、静电效应和卤键效应在立体化学控制的协 同调节作用。对于水相中芳构化酶 StrC 体系下的羟醛缩合/芳构化反应的研 究，支持了在水分子介导下进行羟醛缩合反应构建碳-碳键的可行性，揭示 了 StrC 酶在芳构化过程中的重要作用，突出了氨基酸 Arg104、His117 及 Asp123 在选择反应路径和提高催化效率上的关键作用。通过对三个不同催 化体系下催化碳-碳键构建反应的计算研究，深化了对碳-碳键构建反应机制 的理解，进而指导新型催化剂的设计和碳-碳键的构建。

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