New Reactivity Mediated by Hypervalent Iodine Reagents

我们的研究是在综合方法论领域。合成有机化学面临的巨大挑战是开发新的和有效的策略来构建有价值的分子结构。有机高价碘（HVI）试剂是一种多用途和多功能的化合物，其中碘的固有极性被逆转。在这个提案中，我描述了我的学生和我将如何通过开发新的艾滋病毒介导的化学来推进我们的研究计划。开发含氟化合物的新合成方法具有重要的经济和社会意义，我们将研究将氟纳入有机分子的新策略。首先，我们将开发新的分子重排，以制备传统反应性难以获得的氟化基序。然后，我们将探索新的结构域的氟化，试图产生新的氟化环体系。我们还计划开发HVI催化的环化反应，可以增强包括手性HVI试剂并导致不对称反应。我们还将开发一系列相关的多米诺骨牌氟化和三氟甲基化反应。这将通过修改几个相关的腙氧化反应来实现，其中不同的产品结果将由所使用的起始材料的变化而产生。我们将在新的光引发反应中使用HVI试剂，导致过渡无金属碳-碳键形成过程。一般来说，我们将使用普通的商业发光二极管（led）作为碘化物环化反应中汞灯的替代品。使用LED的一个关键好处是，照射是在没有加热的情况下实现的，这使我们能够分离出热不稳定的产物，否则这些产物会进一步发生反应。LED照射将首次使探索光引发反应中的热不稳定碘化物成为可能。我们将把所学到的理论知识应用到相关含氮化合物的合成中，其中同样不稳定的含氮中间体可能在LED照射下茁壮成长。HVI介导化学的现代前沿是在芳烷中催化的反应，我们将探索这些新的碘化反应作为碘芳烃催化的过程，其中活性HVI物质在原位产生。最后，我们将测试手性HVI试剂和手性碘芳烃催化剂，以发现催化的、不对称的、光引发的环化反应。HVI的反向极性灌输了一种能量驱动力量来经历减少并返回到正常的极性。我们将利用这种氧化潜力来开发通过催化氧化C-H键偶联锻造碳-碳键的新策略。我们将发展催化烯烃芳基化反应，寻求对其更好的基本理解，然后将其扩展到包含杂原子的体系，并寻求烯烃乙烯基化反应的新途径。

Our research is in the field of synthetic methodology. The great challenge in synthetic organic chemistry is developing new and efficient strategies to build valuable molecular architectures. Organic hypervalent iodine (HVI) reagents are a versatile and multifunctional class of compounds in which iodine's inherent polarity is reversed. In this proposal, I describe how my students and I will advance our research program by developing new HVI-mediated chemistry. Developing new syntheses of fluorine-containing compounds is economically and societally important, and we will investigate new strategies for incorporating fluorine into organic molecules. First, we will develop new molecular rearrangements for preparing fluorinated motifs not easily accessed by traditional reactivity. We will then explore the fluorination of new structural domains, trying to generate new classes of fluorinated ring systems. We plan to also develop HVI-catalyzed cyclizations that could be enhanced to include chiral HVI reagents and lead to asymmetric reactions. We will also develop a series of related domino fluorination and trifluoromethylation reactions. This will be achieved by modifying several related hydrazone oxidation reactions, where the diverse product outcomes would arise from variations in the starting materials used. We will use HVI reagents in new photo-initiated reactions, leading to transition metal-free carbon-carbon bond forming processes. In general, we will use common, commercial light-emitting diodes (LEDs) as replacements for mercury lamps in cyclization reactions of iodonium ylides. A key benefit to LED use is that irradiation is achieved without heating, permitting us to isolate thermally unstable products that would have otherwise reacted further. LED irradiation will enable, for the first time, exploration of thermally unstable iodonium ylides in photo-initiated reactions. We will apply the learned theoretical knowledge to the synthesis of related nitrogen-containing compounds, where the similarly unstable nitrogen-containing intermediates may thrive under LED irradiation. The modern frontier of HVI-mediated chemistry is reactions catalytic in aryliodide, and we will explore these new iodonium ylide reactions as iodoarene-catalyzed processes where the active HVI species is generated in situ. Finally, we will test chiral HVI reagents and chiral iodoarene catalysts in these, with the goal of discovering catalytic, asymmetric, photo-initiated cyclization reactions. The inverted polarity of HVI instills an energetic driving force to undergo reduction and return to normal polarization. We will harness this oxidative potential to develop new strategies for forging carbon-carbon bonds via catalytic oxidative C-H bond couplings. We will develop our catalytic alkene arylation reaction, seeking a better fundamental understanding of it, and then expand this to include heteroatom-containing systems, and pursue new avenues of alkene vinylation reactivity.