Asymmetric Umpolung Aldehyde Reactions

提出的工作概述了调查的设计过程，用于形成拥挤，多取代键利用功能基团的极性反转的优势。所研究的反应将依赖于使用手性源的催化量。一旦为关键反应性奠定了基础，我们将把注意力转向将这项研究应用于一些生物活性靶点的快速和立体选择性合成。阿扎斯匹林是一种新型血管生成抑制剂，是抗癌药物的潜在靶点。天冬酰胺A是一种有效的烟碱乙酰胆碱受体拮抗剂。它的立体化学致密，多环结构为我们开发更好，更有效的方法来研究这些分子提供了动力。最后，我们希望在利用自由基形成新键的反应的子领域中开发一种控制绝对立体化学的一般方法。完成这一壮举将为复杂分子组装开辟新的前景，这种组装可以利用自由基在一步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.