手性二胺金属配合物催化亚胺的不对称氢化动力学拆分反应

Kinetic resolution of racemic starting material is one of the powerful protocol for obtaining optically active molecules especially in case which containing a quaternary carbon stereocenter or mutiple chiral centers. However, kinetic resolution of imines via asymmetric hydrogenation are less studied. In this project, we will choose transition metal (Ru, Ir or Rh) complexes of chiral diamines as catalysts, and systematically study the structure-activity/selectivity relationship in the hydrogenation of racemic imines such as 3H-indoles. Then, asymmetric kinetic resolution or asymmetric dynamic kinetic resolution of three types of racemic imines will be investigated in detail with the chiral metal diamine catalysts. The origin of selectivity control of multiple chiral centers in the kinetic resolution of racemic imines will also be studied. Thus, this study will provide efficient and practical protocol for the synthesis of optically active amines and imines bearing a quaternary carbon stereocenter or mutiple chiral centers, which are difficult to access with other metheds.

消旋化合物的不对称催化动力学拆分是获得光学活性手性化合物，尤其是含有季碳或多手性中心手性化合物的重要方法之一。但亚胺的不对称氢化动力学拆分还鲜有文献报道。本项目拟采用手性二胺金属配合物为催化剂，通过对催化剂构效关系的系统研究，发展系列亚胺的高效不对称氢化动力学拆分反应；揭示不对称动力学拆分中多个手性中心选择性控制的本质与规律；建立合成手性胺和手性亚胺，尤其是含有季碳或多个连续手性中心的手性胺化合物的高效和实用的不对称合成新方法。

消旋化合物的不对称催化动力学拆分是获得光学活性手性化合物，尤其是含有季碳或多手性中心手性化合物的重要方法之一。但亚胺的不对称氢化动力学拆分还鲜有文献报道。我们发现，以手性二胺金属配合物为催化剂，可以实现五-七元环亚胺的高效不对称氢化及动力学拆分反应；因而建立了合成手性氮杂胺和手性环内亚胺，尤其是含有季碳或多个连续手性中心的手性氮杂环化合物的高效和实用的不对称合成新方法。通过对催化剂构效关系的系统研究，发现催化剂配阴离子形成氢键能力的强弱，可显著的调控亚胺不对称氢化动力学拆分中多个手性中心的对映选择性和非对映选择性。