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

这是有机与高分子化学项目的更新项目。 Swenton 博士正在研究电极反应作为一种产生新合成反应的手段，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加有效并且可能减少污染，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。其中一部分涉及苯胺衍生物的阳极氧化以及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产生高产率的 1,4-加成产物。在二甲基吡啶存在下，对甲氧基苯胺在甲醇中的阳极氧化是生成醌酰亚胺缩酮的一般途径。这些部分以高产率进行有机锂试剂的 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官能化苯胺的通用方法，而且还可以为许多天然产物中存在的环系统提供新的方法。第二个重点领域集中于从阳极氧化产生的瞬时中间体形成碳-碳键的方法。对2'-取代-4-羟基联苯阳极氧化的研究已经确定了烯属中心与芳族部分氧化产生的中间体的分子内反应中的重要变量。将对该与其他烯属单元和其他溶剂亲核试剂组合的反应进行研究。在这些模型研究中生成的二烯酮类型的路线将为各种天然存在的二烯酮（例如，Pronuciferine）和从 2,5-环己二烯酮生物合成衍生的产品提供有趣的方法。最后，将利用最近开发的对苯二酚醚阳极氧化程序，研究一种有趣的 2,5-环己二酮热路线。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，因此将对取代苯酚转化为二烯酮的直接、温和且有效的方法将补充这些多功能中间体的现有合成方法。

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.