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

这是有机与大分子化学专业的一个更新项目。斯温顿博士正在研究电极反应，将其作为合成复杂天然产物的新合成反应的一种手段。电化学反应的使用可以使合成更有效，潜在的污染更少，因为可以对试剂进行更大的控制。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性质。初步研究表明，两种对甲氧基苯胺衍生物的阳极氧化可形成高收率的1,4加成产物。对甲氧基苯胺在甲醇中有卢丁存在的阳极氧化可作为醌酰亚胺酮的一般途径。这些部分经过1,2-有机锂试剂的加成和1,4-丙二酸阴离子的加成，收率很高。这项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。这些反应不仅是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体系提供新的途径。第二个重点关注的领域是由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研究，确立了烯烃中心与芳烃部分氧化生成中间体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的组合进行研究。在这些模型研究中产生的二烯酮的途径将为各种天然存在的二烯酮（例如，原花氨酸）和由2,5-环己二烯酮生物合成的产品提供有趣的方法。最后，利用最近开发的喹啉醚阳极氧化工艺，研究了一种有趣的热合成2,5-环己二烯酮的方法。由于通过酚偶联反应形成的2,5-环己二烯酮中间体是多种天然产物的生物合成前体，一种直接、温和、高效的将对取代酚转化为二烯酮的方法将补充现有的合成方法。

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.