Directed Reactions of Carbonyl Oxides: A New Approach to Ozonolysis

这个项目将探索化学添加剂在烯烃臭氧化反应中指导产物形成的能力，烯烃臭氧化反应是有机化学中最重要的氧化转化之一。虽然半个多世纪以来，人们就已经知道了羰基氧化物在烯烃臭氧化反应中的核心作用，但能够与这些短暂的中间体反应的试剂的范围仍然极其有限。这项研究的核心假设是，特定添加剂的存在将控制中间羰基氧化物的反应活性，以利于特定产品的形成，其中一些产品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，将研究生成和裂解由羰基氧化物衍生的两性离子，作为“还原”臭氧分解的一种新方法，这是一种不需要单独还原步骤而直接产生羰基产物的过程。其次，将探索在Lewis酸存在下的臭氧化作为一种加强对羰基氧化物的亲核捕获的方法。最后，将探索异臭醚的生成和裂解，以将烯烃直接转化为羧基。通过这一奖项，有机和高分子化学项目支持内布拉斯加州大学林肯分校化学系帕特里克·杜索教授的研究。杜索教授的研究工作围绕着臭氧有机氧化的新方法展开，臭氧是一种从氧气和电力中产生的环境可持续氧化剂。这项研究的预期成果，即扩大烯烃臭氧化在有机合成中的应用，将对制药和农业产生积极的影响。该奖项还将支持共同研究员、马卡莱斯特学院的基思·库瓦塔教授的实验室中对一氧化碳反应性的理论研究。

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.