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

这项有机和大分子化学项目的拨款支持劳伦斯·塞尔教授和弗雷德·乌尔巴赫教授的研究，该研究旨在对铜作为催化剂在有机化合物氧化中的作用进行机制研究。这些过程在生物化学和工业过程中都有深远的影响。使用更简化的模型系统来研究这些多方面的过程，这些过程涉及到铜在催化循环中特定位置的不同氧化态，为了解大自然如何实现这种化学反应提供了相当大的见解。计划研究分为四个部分。第一篇研究了未活化胺的脱氢和-杂原子取代胺的氧化裂解。第二项涉及铜胺氧化酶的模型研究，其中醌介导的转氨化随后是铜介导的氨基酚氧化。第三方面涉及氨基酸及其简单n -酰基衍生物的氧化。第四篇研究了铜介导的c端寡肽氧化n -脱烷基的区域选择性，作为铜酰胺酶将肽酰甘氨酸转化为肽羧胺的可能机制。这些领域的初步研究清楚地表明，在许多情况下，多种反应途径是可能的。计划中的工作包括从以下方面对反应进行更深入和更定量的表征：(1)控制竞争性反应途径的因素；(2)底物结构-反应性效应；(3)改变氧化系统的影响。， Cu(I)-双氧vs. Cu(II)-过硫酸盐vs. Cu(III)！(4)金属配位环境等反应条件的影响。

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.