Anodic Oxidation Studies and Their Applications to Organic Synthesis (Chemistry)

这是有机化学和高分子化学课程中的一个更新项目。斯文顿博士正在研究电极反应，将其作为一种产生合成复杂天然产物的新合成反应的手段。使用电化学反应可以使合成更有效，潜在地减少污染，因为可以对试剂进行更好的控制。该计划由两个主要研究领域组成。一部分涉及苯胺衍生物的阳极氧化以及在这些反应中形成的产物的化学。初步研究表明，1，4-加成产物的高产率是由两个对甲氧基苯胺衍生物的阳极氧化形成的。对甲氧基苯胺在甲醇中的氧化反应是一种合成苯苷酰亚胺酮的一般方法。这些部分高产率地经历了有机锂试剂的1，2-加成和丙二酸阴离子的1，4-加成。这项工作涉及对苯胺阳极氧化的深入研究。对这些阳极氧化产物的化学成分进行了研究。这些反应不仅是获得独特官能化的苯胺的通用方法，而且还将为许多天然产品中存在的环系提供新的途径。第二个重点领域主要集中在从阳极氧化产生的瞬时中间体中形成碳-碳键的方法。通过对2‘-取代-4-羟基联苯的阳极氧化反应的研究，确定了芳香族化合物氧化生成的中间体与烯烃中心分子内反应的重要变量。将对该反应与其他烯烃单元和其他溶剂亲核试剂组合进行研究。在这些模型研究中生成的这种类型的二烯酮的路线将提供有趣的方法来获得各种自然存在的二烯酮(例如，普罗诺西林)和由2，5-环己二烯酮生物合成的产物。最后，我们将利用新近开发的喹酚醚阳极氧化法，研究合成2，5-环己二烯酮的一条有趣的热路线。由于通过酚类偶联反应形成的2，5-环己二烯酮中间体是多种天然产物的生物合成前体，因此直接、温和、高效地将对取代苯酚转化为二烯酮的方法将是对这些用途广泛的中间体现有合成方法的补充。

This is a renewal project in the Organic and Macromolecular Chemistry Program. Dr. Swenton is studying electrode reactions as a means of producing new synthetic reactions for the synthesis of complex natural products. The use of electrochemical reactions can make the synthesis more efficient and potentially less polluting because greater control can be exercised over the reagents. This program is comprised of two major areas of research. One part concerns the anodic oxidation of anilide derivatives and the chemistry of the products formed in these reactions. Preliminary work has established that high yields of 1,4-addition products are formed from anodic oxidation of two p-methoxyanilide derivatives. Anodic oxidation of p-methoxyanilides in methanol in the presence of lutidine serves as a general route to quinone imide ketals. These moieties undergo 1,2- addition of organolithium reagents and 1,4-addition of malonate anion in high yields. The work involves an in-depth study of the anodic oxidation of anilides. The chemistry of the products from these anodic oxidations will be investigated. These reactions not only serve as versatile methods for obtaining uniquely functionalized anilides but also will provide new approaches to ring systems present in many natural products. The second area of major emphasis focuses on methods for carbon-carbon bond formation from transient intermediates generated from anodic oxidation. Studies on the anodic oxidation of 2'-substituted-4- hydroxybiphenyls have established the important variables in the intramolecular reactions of olefinic centers with intermediates generated from oxidation of the aromatic moiety. A study of this reaction with other olefinic units and other solvent nucleophile combinations will be performed. A route to dienones of the type generated in these model studies would offer interesting approaches to a variety of naturally occurring dienones (e.g., Pronuciferine) and products biosynthetically derived from 2,5-cyclohexadienones. Finally, an interesting thermal route to 2,5-cyclohexadienones will be studied, making use of recently developed quinol ether anodic oxidation procedure. Since 2,5-cyclohexadienone intermediates formed via phenolic coupling reactions are the biosynthetic precursors of a wide range of natural products, a direct, mild, and efficient method for conversion of p-substituted phenols to dienones would complement existing synthetic approaches to these versatile intermediates.