electrochemical dication pool: a new strategy to couple alkenes and abundant nucleophiles

项目总结/摘要 氧化烯烃官能化反应是一类基本的有机反应。这些反应 是有价值的，因为它们将容易获得的烯烃起始材料转化成不同的极性官能化的 组然而，支撑常规烯烃氧化反应的设计策略需要 亲电试剂既作为氧化剂又作为新安装的官能团的来源。 这大大限制了使用这些方法可获得的化学多样性。模块化方法， 直接利用丰富的亲核试剂的烯烃氧化是一个长期存在的挑战， 解决方案 这个提议是基于我的小组最近的一项发现，即电化学可以产生一种新的类 烯烃和噻蒽之间的双阳离子加合物，是非常有选择性的亲电介质。我们将 研究如何利用这些加合物来开发一套烯烃氧化反应， 现代合成战术无法实现本研究的三个具体目标是探索不同但 这个新的反应平台的交织方面。 目标1.我们正在提出一种从丰富的前体合成紧张环的策略 目标二。我们正在推进一个氧化烯烃杂双官能化的模块化平台 目标3.我们提出了一种从丰富的前体合成烯丙基胺的策略 通过这项工作开发的方法都解决了一个基本类的长期挑战， 有机反应，烯烃氧化。这些新的反应协议将提供一个扩大和多样化的池 下一代药物和分子探针将从中被发现。

PROJECT SUMMARY/ABSTRACT Oxidative alkene functionalization reactions are a fundamental class of organic reactions. These reactions are valuable because they transform readily accessible alkene starting materials into diverse polar functional groups. However, the design strategies that underpin conventional alkene oxidation reactions require electrophilic reagents that serve as both the oxidant and the source of the newly installed functional group. This substantially limits the chemical diversity accessible using these methodologies. A modular approach to alkene oxidation that directly leverages abundant nucleophiles is a long-standing challenge with no general solutions. This proposal is based on a recent discovery from my group that electrochemistry can generate a new class of dicationic adducts between alkenes and thianthrene that are exceptionally selective dielectrophiles. We will study how these adducts can be exploited to develop a suite of alkene oxidation reactions that are otherwise infeasible with modern synthetic tactics. The three specific aims of this research explore distinct but interwoven aspects of this new reaction platform. Aim 1. We are advancing a strategy for strained ring synthesis from abundant precursors Aim 2. We are advancing a modular platform for oxidative alkene heterodifunctionalization Aim 3. We are advancing a strategy for allylic amine synthesis from abundant precursors The methods developed through this work each address long-standing challenges in a fundamental class of organic reactions, alkene oxidations. These new reaction protocols will offer an expanded and diversified pool of building blocks from which the next generation of drugs and molecular probes will be discovered.