有机催化1-萘偶氮构建轴手性骨架的研究

  轴手性化合物广泛存在于手性配体、有机小分子催化剂、天然产物以及生物活性分子中。随着功能化与多样化的轴手性化合物的不断开发与应用，轴手性化学已经成为手性化学中的热门研究领域，从而使得轴手性化合物的催化不对称合成获得了化学工作者极大的关注并获得了长足的发展。因此，不断开发构建新型轴手性骨架的方法是轴手性化学研究领域中至关重要的课题之一。另一方面，有机小分子催化相对于金属催化与酶催化模式，更加符合绿色化学可持续发展的理念，且有机催化的化学反应通常呈现无重金残留、催化效率与选择性高，条件温和、催化剂回收重复利用方便等诸多优越性。基于此研究背景以及实际需求，本文设计通过以偶氮作为萘环的活化基团，以2-萘酚、吲哚、咔唑为亲核试剂，以手性布朗斯特酸为有机小分子催化剂，通过1-萘偶氮C4位碳氢键不对称官能团化反应，构建新的C-C键或C-N键轴手性骨架，并探索所合成的轴手性化合物的转化与应用。

  为了构建C-C键联芳基轴手性骨架，本论文利用2-萘酚作为芳基化试剂，在手性布朗斯特酸催化下，与咪唑啉酮酰基取代的1-萘偶氮通过不对称交叉偶联反应，实现了1-萘偶氮C4位碳氢键不对称芳基化反应，合成轴手性联萘氨基酚衍生物。底物中咪唑啉酮酰基作为辅基，在提高不对称交叉偶联反应的活性和立体选择性方面起到至关重要的作用。该合成策略在温和的反应条件下以及较短的反应时间内，对于各种类型的常见的取代基（包括烷基、烷氧基、烯基、炔基、(杂)芳环、卤素、酯基、硅醚、硼酸酯和磺酸酯等）修饰的2-萘酚与1-萘偶氮高效地完成不对称交叉偶联反应。通过这一方法，我们成功高效地合成了69种轴手性联萘氨基酚衍生物。这充分表明了该合成方法具有较高的反应活性，并展现出优秀的区域选择性、对映选择性以及广泛的官能团兼容性。此外，对于所合成的轴手性联萘氨基酚，我们通过进一步衍生化反应合成了一系列新型轴手性分子，成功实现了联芳基轴手性产物的多样化转化与应用。

  在手性磷酸催化下，以2-位取代的吲哚类化合物作为亲核试剂，通过1-萘偶氮C4位碳氢键不对称官能团反应构建了C-C键轴手性骨架，高效合成了一系列芳基吲哚类型的轴手性化合物。该反应兼容常见的多种官能团，并能够在短时间内（1-10分钟）快速完成转化，产率高达99%，对映选择性达到99%。此外，在所得芳基吲哚轴手性产物中加入氧化剂可将其转变为偶氮类型原料，并在布朗斯特酸存在下进一步实现1-萘偶氮C2位碳氢键官能团化反应，从而实现了C-S键与C-P键的高效构建，并且产物的对映选择性与原料保持一致。通过DFT理论计算，我们最终阐明了反应经历的历程以及解释了该反应区域选择性控制的来源。

  此外，为了探索C-N键轴手性骨架的不对称构建，我们设计了在手性磷酸的催化下，以咔唑作为胺化试剂，实现1-萘偶氮C4位不对称胺化反应，并成功合成了一系列包含芳基咔唑结构的C-N键轴手性化合物。尽管底物中邻位取代基的存在增强了产物的稳定性，然而咔唑作为亲核试剂，碳氢键胺化反应会面临较大的空间位阻问题，这对于提高反应活性和对映选择性控制都构成不利影响。为解决该问题，在条件优化过程中，我们最终选择了咪唑啉酮酰基取代的1-萘偶氮作为底物，并采用具有大共轭边臂修饰的手性磷酸作为催化剂。其中，底物上引入的咪唑啉酮酰基与手性磷酸之间通过非共价相互作用发挥重要作用，提高了碳氢键不对称胺化反应的活性和对映选择性。

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