不对称钯催化C-C/Si键断裂的双官能化反应及其催化机制研究

手性物质的精准构筑及其相关催化反应机制是均相催化中的核心科学问题之一，仍然存在许多悬而未决的问题，其中基于碳-碳/硅键催化断裂过程精准构建手性中心就一直面临着难以控制、手性转移效率不高等难题。因此，申请人期望基于具挑战性的碳-碳/硅键断裂策略，探索不对称钯催化转化新反应过程：（1）利用廉价易得的手性配体发展出构建含功能化基团或季碳/硅手性中心的高效催化方法，为探索钯催化合成重要手性分子（包括含类似结构单元的手性高分子）提供新策略。（2）利用钯催化活化碳-碳/硅键的独特模式发展出新型高效高选择性双官能化反应，在开发高效的新型催化剂和新反应手性调控上取得原创性成果。（3）在捕获手性高价钯物种及其催化断裂碳-碳/硅键反应的构效关系研究上取得新突破，揭示反应过程中手性产生、传递、放大和调控的机制和规律，阐明手性钯催化剂的结构与功能的关系，以此为依据不断更新设计具有更加完美的立体选择性反应过程。

The precise and stereoselective construction of chiral molecule and material, and its related reaction mechanism are one of the core scientific problems in chiral science. At present, there are still many unresolved problems, including the catalytic asymmetric construction of the carbon stereocenters based on carbon-carbon bond or carbon-silicon bond cleavage has been faced with the difficulty of controlling stereoselectivity and low reaction efficiency. Therefore, the applicants expect to explore a novel and challenging enantioselective palladium-controlled reaction process to construct a new carbon stereocenters based on a desymmetrization strategy through carbon-carbon bond or carbon-silicon bond cleavage: (1) To develop a highly efficient process for stereoselective construction of optically pure substances containing functional groups or quaternary carbon/silicon stereocenters by inexpensive and readily available chiral ligands and palladium catalysis, which will provide new knowledge and technical reserves for exploring catalytic synthesis of important chiral molecules, including chiral polymers containing the same structural units. (2) The determination of unique mode of catalytic activation of carbon-carbon bonds and carbon-silicon bond by palladium for highly efficient bifunctionalization-based ring-opening and ring-expansion reaction, which will be distinctive results in the development of new concepts and strategies for asymmetric catalysis. (3) To achieve a new breakthrough in the study of the structure-activity relationship for asymmetric palladium-catalyzed reactions involving carbon-carbon bond or carbon-silicon bond cleavage, and continue to revealing the mechanism of chirality transfer and chirality amplification in the related reaction. The law established in these works can clarify the relationship between the structure and functionality of the chiral palladium catalyst, and will be beneficial to the design of much more efficient catalyst systems with perfect stereoselectivity in palladium-catalyzed carbon-carbon and carbon-silicon bond activation.