The Reactivity of Metal-Oxo and Metal-Imido Groups

本研究的重点是确定含氧和亚胺功能的过渡金属配合物的基本反应模式。详细的动力学分析的化学计量锇化反应将进行，并辅以电化学研究。在另一组涉及锇催化二羟基化的实验中，x射线晶体学和微量热法将用于提供生物碱配体与烯烃底物之间络合的证据。最后，对烯烃氨基羟基化反应的锇（VIII）催化方法进行了优化。有了这个奖项，合成有机项目支持了克里普斯诊所和研究基金会化学系的K. Barry Sharpless博士的研究。Sharpless教授将专注于阐明含有金属杂原子多键的过渡金属配合物反应性的基本机制。大量的努力将集中在四氧化锇与烯烃在配位叔胺存在下的反应。该反应作为在有机分子中引入立体中心的一种方法而取得了突出的成就。然而，实际上我们对这个过程是如何发生的知之甚少。

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..