手性环戊二烯配体的设计合成及其在不对称C-H键官能团化反应中应用研究

过渡金属催化的不对称C-H键官能团化反应可以减少底物预活化和废弃物产生，显著提高分子的合成效率，是不对称催化合成的前沿热点之一。由于底物中C-H键通常具有相似的化学性质，实现高效不对称C-H键官能团化反应的区域、立体、对映选择性控制极具挑战。项目针对Rh（III）催化不对称C-H键官能团化反应领域中手性配体局限、反应模式单一、催化效率偏低以及选择性不佳等一些亟待解决的问题，设计合成位阻及电性可调的新型手性环戊二烯配体及其铑络合物，发展高效不对称加成、芳基化以及环化等C-H键官能团化反应，实现中心手性、轴手性和螺旋手性化合物的高效高选择性合成，同时探索其在生物活性分子、手性配体或催化剂和手性材料等合成中的应用。

Transitional metal catalyzed asymmetric C-H bond functionalization can avoid the pre-activation of substrates, reduce the production of waste, and significantly improve the synthetic efficiency. It has been one of the emerging frontiers in asymmetric synthesis. Due the existence of a great number of C-H bonds bearing similar chemical environment in an organic molecule, it is very challenging to achieve highly regio-, stereo- and enantioselective C-H bond functionalization. There are still several key issues to be addressed in the field of Rh（III）-catalyzed asymmetric C-H bond functionalization, such as limited chiral ligands and reaction modes, low efficiency and poor selectivity. This project focuses on the design/synthesis of novel chiral cyclopentadiene ligands with tunable steric hindrance and electron properties and their rhodium complexes as well. The highly enantioselective C-H bond functionalization reactions including direct addition, arylation and annulation reactions will be developed to provide structurally diverse central, axial and helical chiral compounds with high efficiency. Their applications in the synthesis of biologically active molecules, chiral ligands/catalysts, and chiral organic materials will also be investigated.