Directed Reactions of Carbonyl Oxides: A New Approach to Ozonolysis

本计画将探讨化学添加剂在烯烃臭氧分解反应中直接形成产物的能力，烯烃臭氧分解反应是有机化学中最重要的氧化转化之一。 虽然羰基氧化物在烯烃臭氧分解中的中心作用已经知道了超过半个世纪，但能够与这些短寿命中间体反应的试剂的范围仍然非常有限。 该研究的核心假设是，特定添加剂的存在将控制中间体羰基氧化物的反应性，以有利于形成特定产物，其中一些产物是传统方法完全无法获得的。 该项目将侧重于三个领域：第一，羰基氧衍生的两性离子的产生和分裂将作为“还原”臭氧分解的新方法进行研究，这是一种直接产生羰基产物而不需要单独的还原步骤的过程。 第二，臭氧分解的存在下，刘易斯酸将探讨作为一种手段，用于提高亲核捕获的羰基氧化物。 最后，杂臭氧化物的产生和断裂将探讨烯烃直接转化为羧基。 有了这个奖项，有机和高分子化学计划是支持教授帕特里克Dussault在化学系在内布拉斯加大学林肯分校的研究。 Dussault教授的研究工作围绕着用臭氧进行有机氧化的新方法，臭氧是一种由氧气和电力产生的环境可持续氧化剂。该研究的预期成果，扩大了烯烃臭氧分解在有机合成中的应用，将对制药和农业工业产生积极影响。 该奖项还将支持在合作研究员Macalester学院的基思桑田教授的实验室中对羰基氧化物反应性的理论研究。

This project will explore the ability of chemical additives to direct the formation of products in alkene ozonolysis, one of the most important oxidative transformations in organic chemistry. While the central role of carbonyl oxides in alkene ozonolysis has been known for more than a half century, the scope of reagents able to react with these short-lived intermediates remains extremely limited. The hypothesis central to the research is that the presence of specific additives will control the reactivity of the intermediate carbonyl oxides to favor formation of particular products, some of which are completely unavailable by traditional methodology. The project will focus on three areas: First, the generation and fragmentation of carbonyl oxide-derived zwitterions will be investigated as a new approach for "reductive" ozonolysis, a process which directly produces carbonyl products without the need for a separate reductive step. Second, ozonolysis in the presence of Lewis acids will be explored as a means for enhancing nucleophilic trapping of carbonyl oxides. Finally, generation and fragmentation of heteroozonides will be explored for the direct conversion of alkenes to carboxyl groups. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Patrick Dussault at the Department of Chemistry at the University of Nebraska-Lincoln. Professor Dussault's research efforts revolve around new methods for organic oxidations with ozone, an environmentally sustainable oxidant generated from oxygen and electricity. The anticipated outcome of the research, expanded applications of alkene ozonolysis in organic synthesis, will have a positive impact on the pharmaceutical and agricultural industries. The award will also support theoretical investigations of carbonyl oxide reactivity in the laboratories of a co-investigator, Professor Keith Kuwata of Macalester College.