手性桥联双脒基稀土配合物的合成及催化性能研究

项目名称： 手性桥联双脒基稀土配合物的合成及催化性能研究

项目编号： No.21502001

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 王芬华

作者单位： 安徽工程大学

项目金额： 21万元

中文摘要： 不对称催化合成是有机化学研究的热点和前沿，开发高效的手性配合物催化剂是此领域的关键。本项目拟合成系列手性桥联双脒基稀土金属胺基、烃基配合物，探索出该类桥联双脒基稀土配合物的有效合成方法，研究配体取代基电子、立体因素对成键和配位形式的影响，开展该类配合物催化α,β-不饱和羰基化合物的膦氢化反应研究，考察其区域选择性及对映选择性，研究配合物催化酮与三甲基硅腈的反应，考察其催化活性和对映选择性，探讨催化反应的机理。通过该项目的研究，可望探索出该类桥联双脒基稀土配合物的合成方法，成键规律及发展高效、高选择性的催化剂，为更好地开发利用我国丰富稀土资源提供理论基础。

中文关键词： 稀土配合物；桥联双脒；手性配体；不对称膦氢化；不对称硅腈化

英文摘要： The catalytic asymmetric synthesis is the hotspot and front of the organic chemistry research. The key problem is to development the effective chiral catalysts in this field. This project aims to synthesize a series of chiral rare-earth metal amido and alkyl complexes incorporating bridged bis(amidinate) ligands. The electronic and steric effects on the bonding and coordination mode of the ligands to rare-earth metals will be investigated. The complexes will be used as catalysts for hydrophosphonylation (hydrophosphinylation) reaction to α,β-unsaturated carbonyl derivatives, considering the effects of the structures of the complexes on the regioselectivity and enantioselectivity. The catalytic activities and enantioselectivity for the cyanosilylation of ketones will be investigated by the chiral complexes. The catalytic mechanism will also be studied. It is expected that synthetic methods for the bridged bis(amidinate) rare-earth complexes, bonding character, high activity and selectivity catalysts will be developed with the accomplishment of the project. This work will provide a theoretical basis for better exploitation and utilization of rich rare-earth resources.

英文关键词： Rare-earth Complex;Brideged Bis(amidinate)s;Chiral Ligand; Asymmetric Hydrophosphonylation (Hydrophosphinylation);Asymmetric Cyanosilyation