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

过渡金属配合物均相催化的合成及机理研究（化学）

• 批准号: 8721972
• 负责人: Iwao Ojima
• 金额: $ 18.88万
• 依托单位: SUNY at Stony Brook
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-06-01 至 1991-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8721972&HistoricalAwards=false
• 关键词: Synthetic; Mechanistic; Studies; Homogenous; Catalysis

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.

这项关于均质催化过渡金属的研究将由有机和大分子化学计划支持。 基于催化系统的新合成工具的开发有可能提供更多经济，无污染的方法，以合成工业和农业的复杂材料。 最终目标是设计和开发多功能的多催化系统，该系统将允许以高度组织的方式以一锅的方式进行多步合成。 该项目包括三个子项目：（i）混合金属催化剂系统的机理研究，重点是CORH（CO）7催化的机理，包括有关这种独特的混合金属复合物在加氢甲基化 - 氨基化 - 氨基苯双键型过程中的行为的高压FT-IR研究； （ii）通过立体化学方法阐明胺化学方法的机理，该方法将解决历史谜团，即在高压氢存在下，通过设计具有严格的空间需求的强度区分可能在高压氢的情况下选择性地缝合了高压氢的酰基cobalt键。 （iii）冠键合中螯合指导的区域和立体控制，这将首次系统地引入螯合控制，以实现羰基化并将其应用于催化不对称的合成。