Synthetic and Mechanistic Studies on the Homogenous Catalysis of Transition Metal Complexes (Chemistry)

这项过渡金属均相催化的研究将得到有机化学和高分子化学计划的支持。基于催化体系的新型合成工具的发展有可能为工农业用复合材料的合成提供更经济、无污染的方法。最终目标是设计和开发多功能多催化剂系统，允许以高度有组织的方式在一锅中进行多步合成。本项目包括三个子项目：(I)混合金属催化剂体系的机理研究，重点是CoRh(CO)7催化机理，包括高压FT-IR研究这种独特的混合金属络合物在氢甲酰化-氨基-羰化过程中的行为；(2)用立体化学方法阐明氨甲酰化反应的机理，这将解开一个历史谜团，即水在高压氢存在下选择性地裂解酰基钴键，通过设计具有严格空间要求的双环中间体，可以明确地区分所提出的可能的反应机理；(3)以螯合作用为导向的区域和立体控制，这将首次系统地对羰化反应引入络合控制，并将其应用于催化不对称合成。

This research on transition metals for homogeneous catalysis will be supported by the Organic and Macromolecular Chemistry Program. The development of new synthetic tools based on catalytic systems has the potential to provide more economic, pollution-free methods for the synthesis of the complex materials for industry and agriculture. The ultimate goal is to design and develop multi-functional multicatalyst systems which will permit multi-step synthesis in one-pot in a highly organized manner. This project includes three sub-projects: (i) mechanistic study of mixed metal catalyst systems focusing on the mechanism of CoRh(CO)7 catalysis including high pressure FT-IR study on the behavior of this unique mixed-metal complex regarding the hydroformylation-amido-carbonylation process; (ii) elucidation of the mechanism of amidocarbonylation by stereochemical approach which will resolve a historical mystery, i.e., water cleaves acylcobalt bond selectively in the presence of high pressure hydrogen, by designing bicyclic intermediates bearing strict steric requirements that can unambiguously distinguish among the possible mechanisms proposed; (iii) chelation-directed regio- and stereocontrol in carbonylations, which will systematically introduce chelation control, for the first time, to carbonylations and apply it to the catalytic asymmetric synthesis.