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

这是一个有机和高分子化学计划的更新项目。Swenton博士正在研究电极反应作为一种产生新的合成反应的手段，用于合成复杂的天然产物。电化学反应的使用可以使合成更有效并且潜在地更少污染，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和在这些反应中形成的产物的化学。初步工作已经确定，高产量的1，4-加成产物是由两种对甲氧基苯胺衍生物的阳极氧化形成的。在二甲基吡啶存在下，对甲氧基苯胺在甲醇中的阳极氧化作为醌酰亚胺缩酮的一般途径。这些部分经历有机锂试剂的1，2-加成和丙二酸阴离子的1，4-加成，产率高。本工作涉及对苯胺的阳极氧化的深入研究。将研究这些阳极氧化产物的化学性质。这些反应不仅可以作为获得独特功能化苯胺的通用方法，而且将为许多天然产物中存在的环系统提供新的方法。第二个主要重点领域集中于从阳极氧化产生的瞬态中间体形成碳-碳键的方法。对2 '-取代-4-羟基联苯的阳极氧化的研究已经确定了烯烃中心与芳香部分氧化产生的中间体的分子内反应中的重要变量。将进行与其它烯烃单元和其它溶剂亲核试剂组合的该反应的研究。在这些模型研究中产生的类型的二烯酮的路线将为各种天然存在的二烯酮（例如，原荷叶碱）和生物合成衍生自2，5-环己二烯酮的产物。最后，一个有趣的热路线2，5-环己二烯酮将研究，利用最近开发的喹啉醚阳极氧化程序。由于通过酚偶联反应形成的2，5-环己二烯酮中间体是广泛的天然产物的生物合成前体，用于将对位取代的酚转化为二烯酮的直接、温和和有效的方法将补充现有的合成这些通用中间体的方法。

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.