Mechanistic Studies of Free Radical Additions and Rearrangements

本研究主要研究有机化合物的自由基氧化反应。同位素标记的过氧化氢将被用来详细说明与生物相关的介质如胶束、脂双层和脂蛋白的自由基氧化机制。能够作为Lewis酸的手性金属络合物将被结合到适当官能化的烯烃上，并以一种新的方式用于对自由基反应的对映选择性。最后，将研究新的自由基共聚合方法，作为化学计量比定义良好的交替共聚物的一条途径。研究生和博士后将被介绍同位素标记化合物的合成和表征，以及这些试剂和其他专门设计的试剂作为反应的机械探针的使用。通过这一奖项，有机和高分子化学项目支持杜克大学Ned Porter博士的研究和教育活动。波特教授将把他的研究重点放在获取有关自由基氧化的基本信息上。有机自由基在不同的生化过程中所起的作用以及它们在有机和材料合成中的应用日益增多，这使得人们有必要阐明这些活性中间体的化学组成。这项研究利用独特的同位素标记分子来探索有机底物的自由基氧化机制，并利用新型有机金属加合物来研究对反应施加立体化学控制的创新方法。波特教授的教育活动包括培养研究生和博士后。U-

This research focuses on the free radical oxidation of organic compounds. Isotopically-labelled hydroperoxides will be used to detail the mechanism of the radical oxidations of biologically relevant media such as micelles, lipid bilayers and lipoproteins. Chiral metal complexes capable of acting as Lewis acids will be bound to appropriately functionalized alkenes and used in a novel manner to impose enantioselectivity on the radical reactions. Lastly, new free radical copolymerization procedures will be examined as a route to stoichiometrically well-defined alternating copolymers. Graduate and postdoctoral students will be introduced to the synthesis and characterization of isotopically-labelled compounds, and the use of these and other specifically designed reagents as mechanistic probes of the reactions. With this award, the Organic and Macromolecular Chemistry Program supports the research and educational activities of Dr. Ned Porter of Duke University. Professor Porter will focus his research on garnering fundamental information on free-radical oxidations. Although known for some time, recognition of the role of organic free radicals in different biochemical processes, as well as their increasing applications in organic and material syntheses creates the need to elucidate the chemistry of these reactive intermediates. This research utilizes unique isotopically-labelled molecules to probe the mechanisms of free radical oxidations of organic substrates, and novel organometallic adducts to examine an innovative approach to imposing stereochemical control on the reactions. Professor Porter's educational activities involve the training of graduate and postdoctoral students. u¬