Development and Applications of Aerobic Electron Transfer Initiated Cyclization Reactions

在化学系有机动力学计划的支持下，匹兹堡大学化学系的Paul Floreancig教授开始了一项计划，在该计划中，电子转移引发的碳-碳西格键激活用于触发新的合成转化。高苯基醚和酰胺是电子转移引发环化(ETIC)反应的起始原料。在这些反应中，底物的光引发单电子氧化形成自由基阳离子中间体，这些中间体通过悬挂的亲核试剂很容易地取代了苯基。提案中描述的项目的最终目标是将ETIC方法发展到足够的程度，使其能够作为有效合成复杂自然项目和其他医学和结构重要化合物的方法。匹兹堡大学化学系的Paul Floreancig教授将在有机动力学计划的支持下，建立新的合成方法，并计划开发对环境影响最小的化学应用，并将ETIC用于酰胺类化合物的合成。这种底物将增加对从南太平洋海绵中分离出来的结构有趣的抗癌药物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.