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

使用金属基试剂形成 C-O 和 C-N 键

• 批准号: 2459320
• 负责人: ROBERT G BERGMAN
• 金额: $ 27.47万
• 依托单位: UNIVERSITY OF CALIFORNIA BERKELEY
• 依托单位国家: 美国
• 财政年份: 1978
• 资助国家: 美国
• 起止时间: 1978-08-01 至 2001-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2459320
• 关键词: catalyst; chemical addition; chemical bond; chemical synthesis; chemical transfer reaction; cyclic compound; ligands; metal complex; nitrogen compounds; organometallic compounds; oxidation; oxygen compounds

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.

金属介导的氧化反应在生物化学中起着重要的作用， 过程和非生物反应中使用的有机合成。 的 这些反应的大部分功能是转移 含有杂原子如氮和氧的基团， 分子。 这些过程中有许多被假定为通过 含有活性金属-氧和金属-氮的金属络合物 债券 然而，对这些官能团的化学性质的理解 它们的反应机制大大落后于 已知涉及金属-碳的类似转化， 金属-氢键 该提案的目标是制定系统的方法， 含有金属-杂原子键的络合物的合成和用于 研究其反应的范围和机制。 这将改善 了解目前已知的金属介导的 氧化/杂原子转移反应并允许合理的 这类反应的新成员的发展。的 该提案概述了实现这些目标的以下方法：（1） 金属配合物合成的一般方法的发展 反应性的金属-氧和-氮单键和多键 对有机化合物;（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， 间接方法表征;（3）反应探索 这些材料与有机化合物;和（4）阐明的 这些反应的机制，以揭示有用的一般概念 理解目前已知的氧化/杂原子转移方法 并用于开发新的催化和化学计量合成 试剂