Development and Applications of Aerobic Electron Transfer Initiated Cyclization Reactions

在化学系有机动力学项目的支持下，匹兹堡大学化学系的Paul Floreancig教授开始了一个项目，在这个项目中，电子转移引发碳-碳sigma键激活，从而触发新的合成转化。同型酶醚和酰胺被用作电子转移引发环化反应的起始原料。在这些反应中，光引发的底物的单电子氧化形成自由基阳离子中间体，这些中间体被悬置的亲核试剂容易取代苄基。提案中描述的项目的最终目标是将ETIC方法推进到足够的程度，使其可以作为一种有效合成复杂天然项目和其他药用和结构重要化合物的方法。匹兹堡大学化学系的Paul Floreancig教授在有机动力学项目的支持下，将建立新的合成方法，并计划开发化学应用，将对环境的影响降到最低，并将ETIC用于酰基胺类化合物的合成。这种底物将增加对从南太平洋海绵中分离出来的结构上有趣的抗癌剂pederin的了解。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Paul Floreancig, of the Department of Chemistry at the University of Pittsburgh, has begun a program in which electron transfer initiated carbon-carbon sigma-bond activation serves to trigger new synthetic transformations. Homobenzylic ethers and amides are used as the starting materials for electron transfer initiated cyclization (ETIC) reactions. In these reactions, photoinitiated single electron oxidation of the substrates form radical cation intermediates that undergo a facile displacement of a benzyl radical by pendent nucleophiles. The ultimate objective of the projects described in the proposal is to advance the ETIC method to a sufficient extent that it can serve as a method for efficient syntheses of complex natural projects and other medicinally and structurally important compounds.Professor Paul Floreancig, of the Department of Chemistry at the University of Pittsburgh, with the support of the Organic Dynamics Program, will establish new synthetic methodology and plans to develop applications of the chemistry, which minimizes impact to the environment and uses ETIC in the synthesis of acylaminals. This substrate will allow increased understanding of the structurally intriguing anticancer agent, pederin, which is isolated from South Pacific sponges.