Copper-Promoted Oxidation and Oxygenation Reactions of Nitrogen-Containing Aliphatic Compounds (Chemistry)

铜促进的含氮脂肪族化合物的氧化和氧化反应（化学）

• 批准号: 8706263
• 负责人: Lawrence Sayre
• 金额: $ 26.35万
• 依托单位: Case Western Reserve University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-07-15 至 1991-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8706263&HistoricalAwards=false
• 关键词: Copper; Promoted; Oxidation; Oxygenation; Reactions

This grant in the Organic and Macromolecular Chemistry Program supports research of Professors Lawrence Sayre and Fred Urbach, which aims at a mechanistic study concerning the role of copper as a catalyst in the oxidation of organic compounds. Such processes have far reaching consequences in both biochemical and industrial processes. The use of more simplified model systems to study these multifaceted processes that involve different oxidation states of copper at specific places in the catalytic cycle provides considerable insight into how nature achieves such chemical reactions. The planned research is divided into four sections. The first examines the dehydrogenation of unactivated amines and the oxidative cleavage of beta-hetero-atom-substituted amines. The second involves a model study for the copper amine oxidases in which a quinone-mediated transamination is followed by copper-mediated oxidation of the resulting aminophenol. The third aspect deals with oxidations of amino acids and simple N-acyl derivatives thereof. The fourth examines the regioselective copper-mediated oxidative N-dealkylation of oligopeptides at the C-terminus as possible mechanisms for the copper amidases which convert peptidylglycine to peptide carboxamides. Initial studies in these areas make it clear that multiple reaction pathways are possible in many cases. The planned work involves a deeper and more quantitative characterization of the reaction in terms of (1) the factors which control competitive reaction pathways, (2) substrate structure-reactivity effects, (3) the effect of varying the oxidation system ?e.g., Cu(I)-dioxygen vs. Cu(II)-peroxydisulfate vs. Cu(III)!, and (4) the effect of the metal coordination environment and other reaction conditions.

有机和高分子化学项目的资助 支持劳伦斯塞尔和弗雷德·乌尔巴赫教授的研究， 其目的是对铜的作用机理进行研究， 作为有机化合物氧化的催化剂。 等 这些过程对生物化学和生物医学都有深远的影响。 和工业过程。 使用更简化的模型 系统来研究这些多方面的过程， 不同的氧化态的铜在特定的地方， 催化循环提供了相当多的见解， 实现这样的化学反应。 计划的研究分为四个部分。 第一 研究了未活化胺的脱氢作用， β-杂原子取代的胺的氧化裂解。 的 第二个涉及铜胺氧化酶的模型研究， 接着是醌介导的转氨作用， 铜介导的对氨基苯酚的氧化。 的 第三方面涉及氨基酸和简单氨基酸的氧化。 其N-酰基衍生物。 第四节审查了 区域选择性铜介导的氧化N-脱烷基化 寡肽在C-末端作为可能的机制， 将肽基甘氨酸转化为肽的铜酰胺酶 羧酰胺。 这些领域的初步研究表明， 在许多情况下，多种反应途径是可能的。 计划中的工作涉及更深入、更量化的 反应的表征（1）因素 控制竞争性反应途径，（2）底物 结构-反应性效应，（3）改变 氧化系统？例如，在一个实施例中，Cu（I）-双氧与 Cu（II）-过二硫酸盐与Cu（III）！，（4）影响 金属配位环境等反应条件。