C-O AND C-N BOND FORMATION USING METAL-BASED REAGENTS

该建议旨在发展基础有机金属化学 利用过渡金属基试剂形成新的 有机分子中的碳-氧（C-O）和碳-氮（C-N）键。 所概述的初始实验被设计为产生用于以下的一般方法： 制备金属-烷氧基、-羟基和氨基络合物。 然后 提出诱导这些物质进行转化（例如， 插入、氧化加成、还原消除）类似于那些 已知的金属烷基络合物，并使用这些基本反应来开发 将负电性配体转移到有机小分子上的方法 底物，如烯烃、炔烃和CO。特别注意的是 具有手性配体亚烷基酰胺配合物的研究 配体，因此可用于制备光学活性胺， 非手性底物 此外，亦概述了拟备及研究 氧杂和氮杂金属杂环在烯烃氧化过程中的作用， 探索开发新型金属基有机氧化的可能性 通过检查低价金属络合物与 控制量的氧化剂如O2、过氧化物和过酸。

This proposal is aimed at developing the basic organometallic chemistry necessary for utilizing transition metal-based reagents to form new carbon-oxygen (C-O) and carbon-nitrogen (C-N) bonds in organic molecules. Initial experiments outlined are designed to yield general methods for the preparation of metal-alkoxy, -hydroxy and amido complexes. It is then proposed to induce such species to undergo transformations (e.g., insertion, oxidative addition, reductive elimination) analogous to those known for metal alkyl complexes, and use these basic reactions to develop ways to transfer the electronegative ligands to organic and small-molecule substrates such as alkenes, alkynes and CO. Special attention is paid to the study of alkylideneamido complexes, which are capable of bearing chiral ligands and thus can be used to prepare optically active amines from achiral substrates. Plans are also outlined to prepare and examine the role of oxa- and azametallacycles in alkene oxidation processes, and to explore the possibility of developing new metal-based organic oxidation reagents by examining the reactions of low-valent metal complexes with controlled amounts of oxidizing agents such as O2, peroxides and peracids.