The Reactivity of Metal-Oxo and Metal-Imido Groups

金属-氧代基团和金属-亚氨基基团的反应性

• 批准号: 9531152
• 负责人: K. Barry Sharpless
• 金额: $ 69.95万
• 依托单位: The Scripps Research Institute
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-04-01 至 2000-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9531152&HistoricalAwards=false
• 关键词: Reactivity; Metal; Oxo; Imido; Groups

The focus of this research is to identify the fundamental modes of reactivity of transition metal complex containing oxo and imido functions. Detailed kinetic analyses of stoichiometric osmylation reactions will be performed, augmented by electrochemical studies. In another set of experiments involving osmium -catalyzed dihydroxylation , X-ray crystallography and microcalorimetry will be used to provide evidence about complexation between alkaloid ligands and olefinic substrates. Finally, the catalytic method for the aminohydroxylation of alkenes via an osmium (VIII) species will be optimized. With this award, the Synthetic Organic Program is supporting the research of Dr. K. Barry Sharpless of the Department of Chemistry at the Scripps Clinic and Research Foundation. Professor Sharpless will focus his work on elucidating the fundamental mechanism of reactivity of transition metals complexes containing metal-heteroatom multiple bonds. A substantial amount of the effort will focus on the reaction of osmium tetroxide with alkenes in the presence of coordinating tertiary amines. This reaction has achieved prominence as a method for the introduction of stereogenic centers into organic molecules. Yet very little is actually known about how this process occurs..

这项研究的重点是确定包含Oxo和Imido功能的过渡金属复合物的反应性基本模式。 通过电化学研究增强了化学计量渗透反应的详细动力学分析。 在另一组涉及渗透性二羟基化的实验中，将使用X射线晶体学和微钙化法来提供有关生物碱配体和烯烃底物之间络合的证据。 最后，将优化通过osmium（VIII）物种氨基羟基化的催化方法。通过该奖项，合成有机计划正在支持Scripps诊所和研究基金会化学系K. Barry Sharpless博士的研究。 Sharpless教授将重点放在阐明含有金属杂质多键的过渡金属复合物的反应性基本机制上。 大量的努力将集中于在辅助三级胺的存在下，四氧化osmmium osmium osmium osmium氧化物与烷烃的反应。 作为将立体中心引入有机分子的方法，该反应已获得突出。 然而，实际上对这个过程的发生知之甚少。