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.

这项关于均相催化的过渡金属的研究将得到有机和高分子化学计划的支持。 基于催化系统的新型合成工具的开发有可能为工农业复杂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，该系统将允许以高度组织的方式在一锅中进行多步合成。 该项目包括三个子项目：(i) 混合金属催化剂体系的机理研究，重点关注 CoRh(CO)7 催化机理，包括对这种独特的混合金属配合物在加氢甲酰化过程中的行为进行高压 FT-IR 研究。酰胺基羰基化过程； (ii) 通过立体化学方法阐明酰胺羰基化的机制，这将解决一个历史谜团，即水在高压氢气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，可以明确地区分可能的机制建议的; （iii）羰基化中螯合定向的区域和立体控制，这将首次系统地将螯合控制引入羰基化并将其应用于催化不对称合成。