New Routes to fluorocarbons using fluoroboranes

氟化分子已经上升到现代科学进步的前沿。从特氟龙到药品（包括立普妥等畅销药物），碳氟键的受控形成带来了革命性的生物和结构效应。然而，目前形成碳氟键的方法通常依赖于高活性的氟源，这限制了广泛的应用和使用。这笔拨款将开发基于硼氟键的氟源，使碳氟键的形成能够使用新的和正交的反应性与目前的方法。硼具有低的生理毒性和环境毒性，是一种可持续的催化材料。这使其成为制药和农业领域应用的理想选择。硼氟键通常被认为是相对惰性的，但我们对硼化学的深入了解将使B-F键的反应性得以开启。该项目将通过合理调整硼的结构来实现这一目标，从而能够从简单、廉价的稳定来源（例如MF）捕获氟，并随后将其转移到简单和复杂的分子框架中。有三种方法可以做到这一点：1。相转移催化;2. 活性底物的氟转移和捕集3. 将氟和硼转移到未活化的底物上。这些方法都有一个共同的主题，即硼氟键的形成和随后的氟转移，但它们不是相互依赖的。每种方法将单独开发，并解决不同的综合需求。相转移催化将氟从固体或水（水）相转移到反应性有机相。硼的结构将用来控制转移的位置和表面选择性。氟转移到活化和未活化底物将利用活化的硼氟键。关键是在接近底物时激活硼-氟键，硼的结构将用于增强这种相互作用并确保硼-氟键的激活。这三种方法将用于探索和理解硼氟键的基本原理，如何影响高产量的氟转移到衬底，以及如何合理地修饰硼烷结构以实现新的反应性。所有这些方法最终将在新的反应性应用于工业相关目标-新的活性药物成分，农药和材料前体。

Fluorinated molecules have risen to the forefront of modern scientific advances. From Teflon to pharmaceuticals (including blockbuster drugs, e.g. Lipitor), the controlled formation of carbon-fluorine bonds has imparted revolutionary biological and structural effects. However, the current methods to form carbon-fluorine bonds generally rely on highly reactive fluorine sources that limit widespread application and use. This grant will develop fluorine sources based on boron-fluorine bonds that enable the formation of carbon-fluorine bonds using new and orthogonal reactivity to current methods. Boron offers a sustainable choice for catalysis with low physiological and environmental toxicity. This makes it an ideal choice for applications in the pharmaceutical and agrichemical sectors. The boron-fluorine bond is usually considered to be relatively inert, but our deep understanding of boron chemistry will enable the reactivity of B-F bonds to be switched on. This project will achieve this by rationally tuning the structure about boron to enable the capture of fluorine from simple, inexpensive stable sources (e.g. MF) and subsequently transfer it to simple and complex molecular frameworks. Three methods to do this have been identified: 1. Phase-transfer Catalysis; 2. Fluorine transfer and trapping of activated substrates; 3. Transfer of fluorine and boron to unactivated substrates. These methods share a common theme of boron-fluorine bond formation and subsequent fluorine transfer, but they are not inter-reliant. Each method will be developed separately and addresses a different synthetic need. Phase-transfer catalysis will take fluorine from the solid or aqueous (water) phase and transfer it to the reactive, organic phase. The structure about boron will be used to control the position and facial selectivity of the transfer. Fluorine transfer to activated and unactivated substrates will exploit an activated boron-fluorine bond. Key to this will be activation of the boron-fluorine bond on approach to the substrate and the structure about boron will be used to enhance this interaction and ensure boron-fluorine bond activation. All three methods will be used to explore and understand the fundamentals of boron-fluorine bonding, how to effect high yielding fluorine transfer to substrates, and how rational modifications to borane structure can be used to enable new reactivity. All of the methods will culminate in the application of the new reactivity to industry relevant targets - new active pharmaceutical ingredients, agrichemicals and materials precursors.