催化不对称去芳构化是一种将简单的平面芳香化合物转化为三维手性分子的简洁高效方法，为天然产物、药物等的合成提供了便利。但目前的报道主要集中于氧化、烯丙基化和烷基化去芳构化等反应，而偶氮化去芳构化和分子间芳基化去芳构化目前尚未见报道。芳基三氮烯因稳定性好、反应位点多及条件温和等优点在有机合成中常作为偶氮化和芳基化试剂，但在不对称合成中的应用尚未实现，特别是经有效调控同时实现不对称偶氮化和芳基化去芳构化反应，可使其成为多样化的“有机合成砌块”，同时填补其在不对称合成中的空白。质子酸、路易斯酸和过渡金属等常用催化剂是调控芳基三氮烯进行多样化转化的关键。基于此，本项目拟通过催化调控芳基三氮烯实现富电子芳烃的不对称偶氮化和芳基化去芳构化反应。以手性质子酸为催化剂，利用手性离子对策略实现不对称偶氮化去芳构化；过渡金属或路易斯酸催化时，利用手性配体诱导实现不对称芳基化去芳构化。

The catalytic asymmetric dearomatization (CADA) reaction is an efficient and simple strategy to convert simple planar aromatic compounds into three-dimensional chiral complex molecules, which provides convenient accesses to various natural products, pharmaceuticals, and their analogues. Although many dearomatization protocols have been developed, however, most of the reported dearomatization reactions are mainly focused on oxidative, allylative and alkylative dearomatization reactions, etc. Furthermore, to the best of our knowledge, no example of an asymmetric diazenylation dearomatization or intermolecular arylation dearomatization reaction has been reported. Although aryltriazenes have been widely used as diazotization and arylation reagents in organic synthesis due to their good stability, diverse transformations and mild reaction conditions, asymmetric synthesis with aryltriazenes have surprisingly not been reported so far. At the same time, by regulating aryltriazene to achieve diazenylation and arylation dearomatization reaction will make it to be a diverse building block, and also achieve its application in asymmetric synthesis. Catalyst plays a crucial role in regulation of aryltriazene for diverse transformations, BrØnsted/Lewis acids and transition metals were often used as catalyst for aryltriazene reaction. Therefore, this proposal is aimed to achieve asymmetric diazenylation and arylation dearomatization reaction of electron-rich aromatics with aryltriazene via chiral BrØnsted/Lewis acid and transition metal catalyst controlled switch. By using chiral BrØnsted acid as catalyst, the formation of chiral ion pair with chiral anion and aryl azo cation is the key step to realize asymmetric diazenylation dearomatization. On the other hand, arylative dearomatizated enantioenriched arylated product will be afforded via chiral ligand controlled Lewis acid or transition metal catalysis.