Novel Radical Reactions for C-C Bond Formation

抽象的。 从容易获得的化学前体构建有价值的复杂分子是本领域的中心目标。 合成.具有生物活性的小分子（包括药物和农用化学品）尤其有价值 因为它们影响人类健康和全球粮食生产。我们的总体研究目标是开发新的 化学反应模式，可用于解决许多不同的和有影响力的问题。 我们的实验室已经开发出一系列基于自由基阴离子的方法， 用于与一系列不同烯烃类型选择性偶联的基质。在这里，我们试图扩展这种机制， 策略来构建许多不同的有价值的复合类。在目标1中，我们提出了一个新的 通过断裂非常强的C-F键制备有价值的氟化化合物的策略 (in芳基三氟甲基）。我们提出了一些不同的方式，激活这些底物， 自由基-阴离子形成可用于键形成过程。目标2寻求利用芳基和杂芳基 自由基阴离子在特权药效团的形成。在目标3中，我们描述了一种新的策略， 非天然肽的合成。

Abstract. The construction of valuable complex molecules from readily available chemical precursors is a central goal in synthesis. Bioactive small molecules (including pharmaceuticals and agrochemicals) are especially valuable because they influence human health and global food production. Our overall research goal is to develop new patterns in chemical reactivity that can be utilized in the solution of many diverse and impactful problems. Our lab has developed a family of radical anion-based processes that selectively activate heteroaromatic substrates for selective coupling with a range of different olefin types. Here we seek to extend this mechanistic strategy to the construction of many different valuable compound classes. In Aim 1, we propose a new strategy for the preparation of valuable fluorinated compounds through the cleavage of very strong C–F bonds (in aryl trifluoromethyl groups). We present a number of different ways that activation of these substrates by radical-anion formation could be utilized in bond-forming processes. Aim 2 seeks to utilize aryl and heteroaryl radical anions in the formation of privileged pharmacophores. In Aim 3, we describe a novel strategy for the synthesis of unnatural peptides.