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

金属介导的氧化反应在生物研究中发挥着重要作用 用于有机合成的过程和非生物反应。这个 这些反应中很大一部分的作用是转移 含有氮和氧等杂原子的基团到有机 分子。这些过程中的许多都被假定通过 含有活性金属氧和金属氮的金属络合物 债券。然而，对这些功能的化学原理的理解 而他们的反应机制远远落后于 已知类似的转变涉及金属-碳和 金属氢键。 这项提议的目标是开发系统的方法来 含金属-杂原子键的络合物的合成 研究它们的反应范围和机理。这将会有所改善 对目前已知的金属介导的机制的理解 氧化剂/杂原子转移反应并允许 发展这类重要反应的新成员。这个 提案概述了实现这些目标的以下方法：(1) 金属络合物合成的一般方法研究进展 具有活性的金属-氧和氮的单键和多键 走向有机化合物；(2)分离和充分表征 这些分子在可能的情况下，在不可能的情况下，它们的 用间接方法表征；(3)反应的探索 这些材料与有机化合物的关系；以及(4)阐明 这些反应的机制，以揭示有助于 了解目前已知的氧化/杂原子转移过程 以及开发新的催化和化学计量比合成 试剂。

Metal-mediated oxidation reactions play an important role in biological processes and in abiological reactions used in organic synthesis. The function of a large proportion of these reactions is the transfer of groups containing heteroatoms such as nitrogen and oxygen to organic molecules. Many of these processes have been postulated to proceed via metal complexes that contain reactive metal-oxygen and metal-nitrogen bonds. However, understanding of the chemistry of these functionalities and the mechanisms of their reactions lags substantially behind what is known about analogous transformations that involve metal-carbon and metal-hydrogen bonds. The goal of this proposal is the development of systematic methods for the synthesis of complexes containing metal-heteroatom bonds and for the study of the scope and mechanisms of their reactions. This will improve understanding of the mechanisms of currently known metal-mediated oxidatiorx/heteroatom transfer reactions and allow the rational development of new members of this important class of reactions. The proposal outlines the following approaches to these goals: (1) development of general methods for the synthesis of metal complexes with metal-oxygen and -nitrogen single and multiple bonds that are reactive toward organic compounds; (2) isolation and full characterization of such molecules where possible, and where it is not, their characterization by indirect methods; (3) exploration of the reactions of these materials with organic compounds; and (4) elucidation of the mechanisms of these reactions to uncover general concepts useful for understanding currently known oxidation/heteroatom transfer processes and for development of new catalytic and stoichiometric synthetic reagents.