Atom- and Group-Transfer Reactions of Nitrous Oxide and Related Molecules

芝加哥大学化学系Gregory L.Hillhouse博士由化学部无机化学、生物无机化学和有机金属化学项目支持，开发一氧化二氮及其相关物种的金属介导反应。将开发利用一氧化二氮、有机叠氮化合物和相关物种进行氧、硫和亚胺基团转移反应的合成方法。这些研究将集中在选择后过渡金属，以便还原消除反应将导致含有氧或氮杂原子的环状有机分子的干净形成。将构建金属催化这些转变的系统。新的硫原子插入后过渡金属-碳键的反应将被设计出来。当今最大的化学挑战之一是有机底物的选择性氧化。一氧化二氮是一种非常有吸引力的氧化剂，它作为氧气转移剂后，只释放无毒和环保的氮气。此外，一氧化二氮被认为既是一种“温室气体”，也是平流层的“臭氧消耗剂”；寻找这种气体的新用途将是有利的，因为它现在是化学工业的一种未得到充分利用的双产品。在这个项目中，将设计金属系统来激活一氧化二氮进行氧原子转移反应，并将开发金属催化剂来促进这些反应。因此，将开发一氧化二氮和一些相关物种的新用途。

Dr. Gregory L. Hillhouse, Chemistry Department, University of Chicago, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division to develop metal mediated reactions of nitrous oxide and related species. Synthetic methods will be developed for oxygen, sulfur, and imido group transfer reactions using nitrous oxide, orgnoazides, and related species. These studies will focus on the late transition metals chosen so that reductive elimination reactions will result in the clean formation of cyclic organic molecules that contain oxygen or nitrogen heteroatoms. Systems will be constructed in which the metal catalyzes these transformations. Novel insertion reactions of sulfur atoms into late transition metal-carbon bonds will be devised. One of today's greatest chemical challenges is the selective oxidation of organic substrates. A very attractive oxidant is nitrous oxide, a molecule which liberates only nontoxic and environmentally friendly nitrogen gas after it serves as an oxygen transfer agent. Moreover, nitrous oxide is recognized as both a `greenhouse gas` and a stratospheric `ozone depleter`; it would be advantageous to find new uses for this gas, which is now an underutilized biproduct of the chemical industry. In this project metal systems will be designed to activate nitrous oxide toward oxygen atom transfer reactions and metal catalysts will be developed to facilitate these reactions. As a result new uses for nitrous oxide and some related species will be developed.