Asymmetric Umpolung Aldehyde Reactions

这项拟议的工作概述了一项关于利用官能团的极性反转来形成稠密的、多重取代键的过程的设计的研究。正在研究的反应将依赖于使用催化量的手性源。一旦为关键反应奠定了基础，我们将把这项研究的重点转向快速和立体选择性地合成一些生物活性靶标。阿司匹林是一种新型的血管生成抑制剂，是抗癌药物的潜在靶点。天冬酰胺A是一种有效的烟碱型乙酰胆碱受体拮抗剂。它的立体化学密度，多环结构为我们提供了一个激励我们开发更好，更有效的方法来处理这些分子。最后，我们希望开发一种通用的方法来控制反应子场中的绝对立体化学，这些反应利用自由基形成新的键。完成这一壮举将在复杂分子组装中开辟新的前景，可以利用自由基在单一步骤中对多个化学转化进行排序的能力。

The proposed work outlines an investigation into the design of processes used to form congested, multiply substituted bonds by taking advantage of a functional group's reversal of polarity. The reactions under investigation will rely on the use of catalytic amounts of a chiral source. Once a foundation for the key reactivity has been laid, we will turn our attention of applying this research to the rapid and stereoselective synthesis of a number of biologically active targets. Azaspirene is a novel angiogenesis inhibitor, a potential target for anti-cancer agents. Asparagamine A is a potent nicotinic acetylcholine receptor antagonist. Its stereochemically dense, polycyclic structure provides an incentive for us to develop a better, more efficient approach to these molecules. Lastly, we hope to develop a general approach to controlling absolute stereochemistry in a subfield of reactions that utilize radicals to form new bonds. Accomplishing this feat would open new vistas in complex molecule assembly that could take advantage of the ability of radicals to sequence multiple chemical transformations in a single step.