手性磷酸催化的不对称合成有机硅烷反应机理的理论研究

近年来，手性有机硅烷因其在官能团化以及衍生化方面的显著反应活性，在功能材料、化学合成和生物活性药物分子开发等领域变得愈发重要。因此，如何通过绿色高效的合成策略获得以硅为手性中心或含硅官能团的对映体纯化合物成为被关注的热点问题。而对新合成策略的开发离不开对反应机理的深入认识。由于含硅的活性中间体在实验中难以捕获及表征，基于量子化学的理论计算研究更为探究手性有机硅烷合成反应机理提供可行性。

本论文系统对比分析了两例以N-三氟甲磺酰基磷酰胺结构为核心的手性Brønsted酸催化体系下手性有机硅烷合成反应的机理路径。一例是谭斌课题组报道的通过手性N-三氟甲磺酰基磷酰胺来活化Si−C_aryl键，进而立体选择性地构建联芳基硅氧烷阻旋异构体；另一例反应体系是由List团队利用亚氨基二磷酸酯催化实现的外消旋烯丙基硅烷的动态动力学不对称转化。两例反应体系都有可能经历两条不同的反应路径，其关键是探究底物被质子化后是倾向于先同催化剂的亲核位点反应生成催化剂-硅活性物种键连中间体，还是在催化剂阴离子形式协助下同亲核试剂发生直接的亲核取代。在对两例反应的机理路径进行深入计算研究后，本文发现两例反应体系都倾向于质子化后直接与亲核试剂醇或酚发生亲核取代。在提出与实验组不同机理猜想的同时，本研究也探讨了手性磷酰胺以分子内异构体磷酰氢形式的新质子化路径的理论可能。本论文详细研究了边臂基团对称性对产物对映选择性的影响，并阐明了联芳基硅氧烷阻旋异构体对映选择性主要来源于催化剂边臂基团与底物之间的CH-π弱相互作用。

本研究深化了对N-三氟甲磺酰基磷酰胺类手性Brønsted酸催化剂活性位点的理解，为此类有机催化手性有机硅烷的化学合成机理做出理论补充，切实为其制备方法的开发与改进提供了理论依据。

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